Continuous Methods for Treating Liquids and Manufacturing Certain Constituents (e.g., Nanoparticles) in Liquids, Apparatuses and Nanoparticles and Nanoparticle/Liquid Solution(s) Resulting Therefrom

ABSTRACT

This invention relates generally to novel methods and novel devices for the continuous manufacture of nanoparticles, microparticles and nanoparticle/liquid solution(s). The nanoparticles (and/or micron-sized particles) comprise a variety of possible compositions, sizes and shapes. The particles (e.g., nanoparticles) are caused to be present (e.g., created and/or the liquid is predisposed to their presence (e.g., conditioned)) in a liquid (e.g., water) by, for example, preferably utilizing at least one adjustable plasma (e.g., created by at least one AC and/or DC power source), which plasma communicates with at least a portion of a surface of the liquid. At least one subsequent and/or substantially simultaneous adjustable electrochemical processing technique is also preferred. Multiple adjustable plasmas and/or adjustable electrochemical processing techniques are preferred. The continuous process causes at least one liquid to flow into, through and out of at least one trough member, such liquid being processed, conditioned and/or effected in said trough member(s). Results include constituents formed in the liquid including micron-sized particles and/or nanoparticles (e.g., metallic-based nanoparticles) of novel size, shape, composition, zeta potential and properties present in a liquid.

The present application is a divisional of U.S. application Ser. No.14/010,721, filed on Aug. 27, 2013 (now U.S. Pat. No. 9,387,452), whichis a divisional of U.S. application Ser. No. 12/686,815, filed on Jan.13, 2010 (now U.S. Pat. No. 8,540,942). The aforementioned presentapplication claims priority to U.S. Provisional Patent Application No.61/144,625, filed on Jan. 14, 2009. All of the applications mentionedabove are hereby expressly incorporated by reference.

FIELD OF THE INVENTION

This invention relates generally to novel methods and novel devices forthe continuous manufacture of nanoparticles, microparticles andnanoparticle/liquid solution(s). The nanoparticles (and/or micron-sizedparticles) comprise a variety of possible compositions, sizes andshapes. The particles (e.g., nanoparticles) are caused to be present(e.g., created and/or the liquid is predisposed to their presence (e.g.,conditioned)) in a liquid (e.g., water) by, for example, preferablyutilizing at least one adjustable plasma (e.g., created by at least oneAC and/or DC power source), which plasma communicates with at least aportion of a surface of the liquid. At least one subsequent and/orsubstantially simultaneous adjustable electrochemical processingtechnique is also preferred. Multiple adjustable plasmas and/oradjustable electrochemical processing techniques are preferred. Thecontinuous process causes at least one liquid to flow into, through andout of at least one trough member, such liquid being processed,conditioned and/or effected in said trough member(s). Results includeconstituents formed in the liquid including micron-sized particlesand/or nanoparticles (e.g., metallic-based nanoparticles) of novel size,shape, composition, zeta potential and properties present in a liquid.

BACKGROUND OF THE INVENTION

Many techniques exist for the production of nanoparticles includingtechniques set forth in “Recent Advances in the Liquid-Phase Synthesesof Inorganic Nanoparticles” written by Brian L. Cushing, Vladimire L.Kolesnichenko and Charles J. O'Connor; and published in ChemicalReviews, volume 104, pages 3893-3946 in 2004 by the American ChemicalSociety; the subject matter of which is herein expressly incorporated byreference.

Further, the article “Chemistry and Properties of Nanocrystals ofDifferent Shapes” written by Clemens Burda, Xiaobo Chen, Radha Narayananand Mostafa A. El-Sayed; and published in Chemical Reviews, volume 105,pages 1025-1102 in 2005 by the American Chemical Society; disclosesadditional processing techniques, the subject matter of which is hereinexpressly incorporated by reference.

The article “Shape Control of Silver Nanoparticles” written by BenjaminWiley, Yugang Sun, Brian Mayers and Younan Xia; and published inChemistry—A European Journal, volume 11, pages 454-463 in 2005 byWiley-VCH; discloses additional important subject matter, the subjectmatter of which is herein expressly incorporated by reference.

Still further, U.S. Pat. No. 7,033,415, issued on Apr. 25, 2006 toMirkin et al., entitled Methods of Controlling Nanoparticle Growth; andU.S. Pat. No. 7,135,055, issued on Nov. 14, 2006, to Mirkin et al.,entitled Non-Alloying Core Shell Nanoparticles; both disclose additionaltechniques for the growth of nanoparticles; the subject matter of bothare herein expressly incorporated by reference.

Moreover, U.S. Pat. No. 7,135,054, which issued on Nov. 14, 2006 to Jinet al., and entitled Nanoprisms and Method of Making Them; is alsoherein expressly incorporated by reference.

The present invention has been developed to overcome a variety ofdeficiencies/inefficiencies present in known processing techniques andto achieve a new and controllable process for making nanoparticles of avariety of shapes and sizes and/or new nanoparticle/liquid materials notbefore achievable.

SUMMARY OF THE INVENTION

This invention relates generally to novel methods and novel devices forthe continuous manufacture of a variety of constituents in a liquidincluding micron-sized particles, nanoparticles, ionic species andnanoparticle/liquid(s) solution(s). The constituents and nanoparticlesproduced can comprise a variety of possible compositions, sizes andshapes, which exhibit a variety of novel and interesting physical,catalytic, biocatalytic and/or biophysical properties. The liquid(s)used and created/modified during the process play an important role inthe manufacturing of, and/or the functioning of the micron-sizedparticles and the nanoparticles. The particles (e.g., nanoparticles) arecaused to be present (e.g., created and/or the liquid is predisposed totheir presence (e.g., conditioned)) in at least one liquid (e.g., water)by, for example, preferably utilizing at least one adjustable plasma(e.g., created by at least one AC and/or DC power source), whichadjustable plasma communicates with at least a portion of a surface ofthe liquid. Metal-based electrodes of various composition(s) and/orunique configurations are preferred for use in the formation of theadjustable plasma(s), but non-metallic-based electrodes can also beutilized. Utilization of at least one subsequent and/or substantiallysimultaneous adjustable electrochemical processing technique is alsopreferred. Metal-based electrodes of various composition(s) and/orunique configurations are preferred for use in the electrochemicalprocessing technique(s). Electric fields, magnetic fields,electromagnetic fields, electrochemistry, pH, zeta potential, etc., arejust some of the variables that can be positively effected by theadjustable plasma(s) and/or adjustable electrochemical processingtechnique(s). Multiple adjustable plasmas and/or adjustableelectrochemical techniques are preferred to achieve many of theprocessing advantages of the present invention, as well as many of thenovel compositions which result from practicing the teachings of thepreferred embodiments. The overall process is a continuous process,having many attendant benefits, wherein at least one liquid, for examplewater, flows into, through and out of at least one trough member andsuch liquid is processed, conditioned, modified and/or effected by saidat least one adjustable plasma and/or said at least one adjustableelectrochemical technique. The results of the continuous processinginclude new constituents in the liquid, micron-sized particles,nanoparticles (e.g., metallic-based nanoparticles) of novel size, shape,composition, zeta potential and/or properties suspended in a liquid,such nanoparticle/liquid mixture being produced in an efficient andeconomical manner.

Certain processing enhancers may also be added to or mixed with theliquid(s). The processing enhancers include both solids and liquids. Theprocessing enhancer may provide certain processing advantages and/ordesirable final product characteristics.

The phrase “trough member” is used throughout the text. This phraseshould be understood as meaning a large variety of fluid handlingdevices including, pipes, half pipes, channels or grooves existing inmaterials or objects, conduits, ducts, tubes, chutes, hoses and/orspouts, so long as such are compatible with the process disclosedherein.

Additional processing techniques such as applying certain crystal growthtechniques disclosed in copending patent application entitled Methodsfor Controlling Crystal Growth, Crystallization, Structures and Phasesin Materials and Systems; which was filed on Mar. 21, 2003, and waspublished by the World Intellectual Property Organization underpublication number WO 03/089692 on Oct. 30, 2003 and the U.S. NationalPhase application, which was filed on Jun. 6, 2005, and was published bythe United States Patent and Trademark Office under publication number20060037177 on Feb. 23, 2006 (the inventors of each being Bentley J.Blum, Juliana H. J. Brooks and Mark G. Mortenson). The subject matter ofboth applications is herein expressly incorporated by reference. Theseapplications teach, for example, how to grow preferentially one or morespecific crystals or crystal shapes from solution. Further, drying,concentrating and/or freeze drying can also be utilized to remove atleast a portion of, or substantially all of, the suspending liquid,resulting in, for example, dehydrated nanoparticles.

An important aspect of one embodiment of the invention involves thecreation of an adjustable plasma, which adjustable plasma is locatedbetween at least one electrode positioned adjacent to (e.g., above) atleast a portion of the surface of a liquid and at least a portion of thesurface of the liquid itself. The liquid is placed into electricalcommunication with at least one second electrode (or a plurality ofsecond electrodes) causing the surface of the liquid to function as anelectrode helping to form the adjustable plasma. This configuration hascertain characteristics similar to a dielectric barrier dischargeconfiguration, except that the surface of the liquid is an activeelectrode participant in this configuration.

Each adjustable plasma utilized can be located between the at least oneelectrode located above a surface of the liquid and a surface of theliquid due to at least one electrically conductive electrode beinglocated somewhere within (e.g., at least partially within) the liquid.At least one power source (in a preferred embodiment, at least onesource of volts and amps such as a transformer) is connectedelectrically between the at least one electrode located above thesurface of the liquid and the at least one electrode contacting thesurface of the liquid (e.g., located at least partially, orsubstantially completely, within the liquid). The electrode(s) may be ofany suitable composition and suitable physical configuration (e.g., sizeand shape) which results in the creation of a desirable plasma betweenthe electrode(s) located above the surface of the liquid and at least aportion of the surface of the liquid itself.

The applied power (e.g., voltage and amperage) between the electrode(s)(e.g., including the surface of the liquid functioning as at least oneelectrode for forming the plasma) can be generated by any suitablesource (e.g., voltage from a transformer) including both AC and DCsources and variants and combinations thereof. Generally, the electrodeor electrode combination located within (e.g., at least partially belowthe surface of the liquid) takes part in the creation of a plasma byproviding voltage and current to the liquid or solution, however, theadjustable plasma is actually located between at least a portion of theelectrode(s) located above the surface of the liquid (e.g., at a tip orpoint thereof) and one or more portions or areas of the liquid surfaceitself. In this regard, the adjustable plasma can be created between theaforementioned electrodes (i.e., those located above at least a portionof the surface of the liquid and a portion of the liquid surface itself)when a breakdown voltage of the gas or vapor around and/or between theelectrode(s) and the surface of the liquid is achieved or maintained.

In one preferred embodiment of the invention, the liquid compriseswater, and the gas between the surface of the water and the electrode(s)above the surface of the water (i.e., that gas or atmosphere that takespart in the formation of the adjustable plasma) comprises air. The aircan be controlled to contain various different water content(s) or adesired humidity which can result in different compositions, sizesand/or shapes of nanoparticles being produced according to the presentinvention (e.g., different amounts of certain constituents in theadjustable plasma and/or in the solution can be a function of the watercontent in the air located above the surface of the liquid) as well asdifferent processing times, etc.

The breakdown electric field at standard pressures and temperatures fordry air is about 3 MV/m or about 30 kV/cm. Thus, when the local electricfield around, for example, a metallic point exceeds about 30 kV/cm, aplasma can be generated in dry air. Equation (1) gives the empiricalrelationship between the breakdown electric field “E_(c)” and thedistance “d” (in meters) between two electrodes:

$\begin{matrix}{E_{c} = {3000 + {\frac{1.35}{d}{kV}\text{/}m}}} & {{Equation}\mspace{14mu} 1}\end{matrix}$

Of course, the breakdown electric field “E_(c)” will vary as a functionof the properties and composition of the gas located between electrodes.In this regard, in one preferred embodiment where water is the liquid,significant amounts of water vapor can be inherently present in the airbetween the “electrodes” (i.e., between the at least one electrodelocated above the surface of the water and the water surface itselfwhich is functioning as one electrode for plasma formation) and suchwater vapor should have an effect on at least the breakdown electricfield required to create a plasma therebetween. Further, a higherconcentration of water vapor can be caused to be present locally in andaround the created plasma due to the interaction of the adjustableplasma with the surface of the water. The amount of “humidity” presentin and around the created plasma can be controlled or adjusted by avariety of techniques discussed in greater detail later herein.Likewise, certain components present in any liquid can form at least aportion of the constituents forming the adjustable plasma locatedbetween the surface of the liquid and the electrode(s) located adjacent(e.g., along) the surface of the liquid. The constituents in theadjustable plasma, as well as the physical properties of the plasma perse, can have a dramatic influence on the liquid, as well as on certainof the processing techniques (discussed in greater detail later herein).

The electric field strengths created at and near the electrodes aretypically at a maximum at a surface of an electrode and typicallydecrease with increasing distance therefrom. In cases involving thecreation of an adjustable plasma between a surface of the liquid and theat least one electrode(s) located adjacent to (e.g., above) the liquid,a portion of the volume of gas between the electrode(s) located above asurface of a liquid and at least a portion of the liquid surface itselfcan contain a sufficient breakdown electric field to create theadjustable plasma. These created electric fields can influence, forexample, behavior of the adjustable plasma, behavior of the liquid,behavior of constituents in the liquid, etc.

In this regard, FIG. 1A shows one embodiment of a point source electrode1 having a triangular cross-sectional shape located a distance “x” abovethe surface 2 of a liquid 3 flowing, for example, in the direction “F”.An adjustable plasma 4 can be generated between the tip or point 9 ofthe electrode 1 and the surface 2 of the liquid 3 when an appropriatepower source 10 is connected between the point source electrode 1 andthe electrode 5, which electrode 5 communicates with the liquid 3 (e.g.,is at least partially below the surface 2 of the liquid 3). It should benoted that under certain conditions the tip 9′ of the electrode 5 mayactually be located physically slightly above the bulk surface 2 of theliquid 3, but the liquid still communicates with the electrode through aphenomenon known as “Taylor cones”. Taylor cones are discussed in U.S.Pat. No. 5,478,533, issued on Dec. 26, 1995 to Inculet, entitled Methodand Apparatus for Ozone Generation and Treatment of Water, the subjectmatter of which is herein expressly incorporated by reference. In thisregard, FIG. 1B shows an electrode configuration similar to that shownin FIG. 1A, except that a Taylor cone “T” is utilized for electricalconnection between the electrode 5 and the surface 2 (or actually theeffective surface 2′) of the liquid 3. The creation and use of Taylorcones is discussed in greater detail elsewhere herein.

The adjustable plasma region 4, created in the embodiment shown in FIG.1A can typically have a shape corresponding to a cone-like structure forat least a portion of the process, and in some embodiments of theinvention, can maintain such cone-like shape for substantially all ofthe process. The volume, intensity, constituents (e.g., composition),activity, precise locations, etc., of the adjustable plasma(s) 4 willvary depending on a number of factors including, but not limited to, thedistance “x”, the physical and/or chemical composition of the electrode1, the shape of the electrode 1, the power source 10 (e.g., DC, AC,rectified AC, the applied polarity of DC and/or rectified AC, RF, etc.),the power applied by the power source (e.g., the volts applied, the ampsapplied, electron velocity, etc.) the frequency and/or magnitude of theelectric and/or magnetic fields created by the power source applied orambient, electric, magnetic or electromagnetic fields, acoustic fields,the composition of the naturally occurring or supplied gas or atmosphere(e.g., air, nitrogen, helium, oxygen, ozone, reducing atmospheres, etc.)between and/or around the electrode 1 and the surface 2 of the liquid 3,temperature, pressure, volume, flow rate of the liquid 3 in thedirection “F”, spectral characteristics, composition of the liquid 3,conductivity of the liquid 3, cross-sectional area (e.g., volume) of theliquid near and around the electrodes 1 and 5, (e.g., the amount of timethe liquid 3 is permitted to interact with the adjustable plasma 4 andthe intensity of such interactions), the presence of atmosphere flow(e.g., air flow) at or near the surface 2 of the liquid 3 (e.g., fan(s)or atmospheric movement means provided) etc., (discussed in more detaillater herein).

The composition of the electrode(s) 1 involved in the creation of theadjustable plasma(s) 4 of FIG. 1A, in one preferred embodiment of theinvention, are metal-based compositions (e.g., metals such as platinum,gold, silver, zinc, copper, titanium, and/or alloys or mixtures thereof,etc.), but the electrodes 1 and 5 may be made out of any suitablematerial compatible with the various aspects (e.g., processingparameters) of the inventions disclosed herein. In this regard, whilethe creation of a plasma 4 in, for example, air above the surface 2 of aliquid 3 (e.g., water) will, typically, produce at least some ozone, aswell as amounts of nitrogen oxide and other components (discussed ingreater detail elsewhere herein). These produced components can becontrolled and may be helpful or harmful to the formation and/orperformance of the resultant nanoparticles and/or nanoparticle/solutionsproduced and may need to be controlled by a variety of differenttechniques, discussed in more detail later herein. Further, the emissionspectrum of each plasma 4 is also a function of similar factors(discussed in greater detail later herein). As shown in FIG. 1A, theadjustable plasma 4 actually contacts the surface 2 of the liquid 3. Inthis embodiment of the invention, material (e.g., metal) from theelectrode 1 may comprise a portion of the adjustable plasma 4 (e.g., andthus be part of the emission spectrum of the plasma) and may be caused,for example, to be “sputtered” onto and/or into the liquid 3 (e.g.,water). Accordingly, when metal(s) are used as the electrode(s) 1,elementary metal(s), metal ions, Lewis acids, Bronsted-Lowry acids,metal oxides, metal nitrides, metal hydrides, metal hydrates and/ormetal carbides, etc., can be found in the liquid 3 (e.g., for at least aportion of the process and may be capable of being involved insimulations/subsequent reactions), depending upon the particular set ofoperating conditions associated with the adjustable plasma 4. Suchconstituents may be transiently present or may be semi-permanent orpermanent. If such constituents are transient or semi-permanent, thenthe timing of subsequent reactions with such formed constituents caninfluence final products produced. Further, depending on, for example,electric, magnetic and/or electromagnetic field strength in and aroundthe liquid 3 and the volume of liquid 3 (discussed in greater detailelsewhere herein), the physical and chemical construction of theelectrode(s) 1 and 5, atmosphere (naturally occurring or supplied),liquid composition, greater or lesser amounts of electrode(s)materials(s) (e.g., metal(s) or derivatives of metals) may be found inthe liquid 3. In certain situations, the material(s) (e.g., metal(s) ormetal(s) composite(s)) or constituents (e.g., Lewis acids,Bronsted-Lowry acids, etc.) found in the liquid 3, or in the plasma 4,may have very desirable effects, in which case relatively large amountsof such materials will be desirable; whereas in other cases, certainmaterials found in the liquid 3 (e.g., by-products) may have undesirableeffects, and thus minimal amounts of such materials may be desired inthe liquid-based final product. Accordingly, electrode composition canplay an important role in the material that is formed according to theembodiments disclosed herein. The interplay between these components ofthe invention are discussed in greater detail later herein.

Still further, the electrode(s) 1 and 5 may be of similar chemicalcomposition and/or mechanical configuration or completely differentcompositions in order to achieve various compositions and/or structuresof liquids and/or specific effects discussed later herein.

The distance between the electrode(s) 1 and 5; or 1 and 1 (shown laterherein) or 5 and 5 (shown later herein) is one important aspect of theinvention. In general, the location of the smallest distance “y” betweenthe closest portions of the electrode(s) used in the present inventionshould be greater than the distance “x” in order to prevent anundesirable arc or formation of an unwanted corona or plasma occurringbetween the electrode (e.g., the electrode(s) 1 and the electrode(s) 5)(unless some type of electrical insulation is provided therebetween).Features of the invention relating to electrode design, electrodelocation and electrode interactions between a variety of electrodes arediscussed in greater detail later herein.

The power applied through the power source 10 may be any suitable powerwhich creates a desirable adjustable plasma 4 under all of the processconditions of the present invention. In one preferred mode of theinvention, an alternating current from a step-up transformer (discussedin greater detail later herein) is utilized. In another preferredembodiment, a rectified AC source creates a positively charged electrode1 and a negatively charged surface 2 of the liquid 3. In anotherpreferred embodiment, a rectified AC source creates a negatively chargedelectrode 1 and a positively charged surface 2 of the liquid 3. Further,other power sources such as RF power sources are also useable with thepresent invention. In general, the combination of electrode(s)components 1 and 5, physical size and shape of the electrode(s) 1 and 5,electrode manufacturing process, mass of electrodes 1 and/or 5, thedistance “x” between the tip 9 of electrode 1 above the surface 2 of theliquid 3, the composition of the gas between the electrode tip 9 and thesurface 2, the flow rate and/or flow direction “F” of the liquid 3, theamount of liquid 3 provided, type of power source 10, frequency of powersource 10, all contribute to the design, and thus power requirements(e.g., breakdown electric field) required to obtain a controlled oradjustable plasma 4 between the surface 2 of the liquid 3 and theelectrode tip 9.

In further reference to the configurations shown in FIG. 1A, electrodeholders 6 a and 6 b are capable of being lowered and raised by anysuitable means (and thus the electrodes are capable of being lowered andraised). For example, the electrode holders 6 a and 6 b are capable ofbeing lowered and raised in and through an insulating member 8 (shown incross-section). The mechanical embodiment shown here include male/femalescrew threads. The portions 6 a and 6 b can be covered by, for example,additional electrical insulating portions 7 a and 7 b. The electricalinsulating portions 7 a and 7 b can be any suitable material (e.g.,plastic, polycarbonate, poly (methyl methacrylate), polystyrene,acrylics, polyvinylchloride (PVC), nylon, rubber, fibrous materials,etc.) which prevent undesirable currents, voltage, arcing, etc., thatcould occur when an individual interfaces with the electrode holders 6 aand 6 b (e.g., attempts to adjust the height of the electrodes).Likewise, the insulating member 8 can be made of any suitable materialwhich prevents undesirable electrical events (e.g., arcing, melting,etc.) from occurring, as well as any material which is structurally andenvironmentally suitable for practicing the present invention. Typicalmaterials include structural plastics such as polycarbonates, plexiglass(poly (methyl methacrylate), polystyrene, acrylics, and the like.Additional suitable materials for use with the present invention arediscussed in greater detail elsewhere herein.

FIG. 1C shows another embodiment for raising and lowering the electrodes1, 5. In this embodiment, electrical insulating portions 7 a and 7 b ofeach electrode are held in place by a pressure fit existing between thefriction mechanism 13 a, 13 b and 13 c, and the portions 7 a and 7 b.The friction mechanism 13 a, 13 b and 13 c could be made of, forexample, spring steel, flexible rubber, etc., so long as sufficientcontact is maintained therebetween.

Preferred techniques for automatically raising and/or lowering theelectrodes 1, 5 are discussed later herein. The power source 10 can beconnected in any convenient electrical manner to the electrodes 1 and 5.For example, wires 11 a and 11 b can be located within at least aportion of the electrode holders 6 a, 6 b (and/or electrical insulatingportions 7 a, 7 b) with a primary goal being achieving electricalconnections between the portions 11 a, 11 b and thus the electrodes 1,5.

FIG. 2A shows another schematic of a preferred embodiment of theinvention, wherein an inventive control device 20 is connected to theelectrodes 1 and 5, such that the control device 20 remotely (e.g., uponcommand from another device) raises and/or lowers the electrodes 1, 5relative to the surface 2 of the liquid 3. The inventive control device20 is discussed in more detail later herein. In this one preferredaspect of the invention, the electrodes 1 and 5 can be, for example,remotely lowered and controlled, and can also be monitored andcontrolled by a suitable controller or computer (not shown in FIG. 2A)containing a software program (discussed in detail later herein). Inthis regard, FIG. 2B shows an electrode configuration similar to thatshown in FIG. 2A, except that a Taylor Cone “T” is utilized forelectrical connection between the electrode 5 and the surface 2 (oreffective surface 2′) of the liquid 3. Accordingly, the embodimentsshown in FIGS. 1A, 1B, and 1C should be considered to be a manuallycontrolled apparatus for use with the techniques of the presentinvention, whereas the embodiments shown in FIGS. 2A and 2B should beconsidered to include an automatic apparatus or assembly which canremotely raise and lower the electrodes 1 and 5 in response toappropriate commands. Further, the FIG. 2A and FIG. 2B preferredembodiments of the invention can also employ computer monitoring andcomputer control of the distance “x” of the tips 9 of the electrodes 1(and tips 9′ of the electrodes 5) away from the surface 2 (discussed ingreater detail later herein). Thus, the appropriate commands for raisingand/or lowering the electrodes 1 and 5 can come from an individualoperator and/or a suitable control device such as a controller or acomputer (not shown in FIG. 2A).

FIG. 3A corresponds in large part to FIGS. 2A and 2B, however, FIGS. 3B,3C and 3D show various alternative electrode configurations that can beutilized in connection with certain preferred embodiments of theinvention. FIG. 3B shows essentially a mirror image electrode assemblyfrom that electrode assembly shown in FIG. 3A. In particular, as shownin FIG. 3B, with regard to the direction “F” corresponding to the flowdirection of the liquid 3, the electrode 5 is the first electrode whichcommunicates with the fluid 3 when flowing in the longitudinal direction“F” and contact with the plasma 4 created at the electrode 1 follows.FIG. 3C shows two electrodes 5 a and 5 b located within the fluid 3.This particular electrode configuration corresponds to another preferredembodiment of the invention. In particular, as discussed in greaterdetail herein, the electrode configuration shown in FIG. 3C can be usedalone, or in combination with, for example, the electrode configurationsshown in FIGS. 3A and 3B. Similarly, a fourth possible electrodeconfiguration is shown in FIG. 3D. In this FIG. 3D, no electrode(s) 5are shown, but rather only electrodes 1 a and 1 b are shown. In thiscase, two adjustable plasmas 4 a and 4 b are present between theelectrode tips 9 a and 9 b and the surface 2 of the liquid 3. Thedistances “xa” and “xb” can be about the same or can be substantiallydifferent, as long as each distance “xa” and “xb” does not exceed themaximum distance for which a plasma 4 can be formed between theelectrode tips 9 a/9 b and the surface 2 of the liquid 3. As discussedabove, the electrode configuration shown in FIG. 3D can be used alone,or in combination with one or more of the electrode configurations shownin FIGS. 3A, 3B and 3C. The desirability of utilizing particularelectrode configurations in combination with each other with regard tothe fluid flow direction “F” is discussed in greater detail laterherein.

Likewise, a set of manually controllable electrode configurations,corresponding generally to FIG. 1A, are shown in FIGS. 4A, 4B, 4C and4D, all of which are shown in a partial cross-sectional view.Specifically, FIG. 4A corresponds to FIG. 1A. Moreover, FIG. 4Bcorresponds in electrode configuration to the electrode configurationshown in FIG. 3B; FIG. 4C corresponds to FIG. 3C and FIG. 4D correspondsto FIG. 3D. In essence, the manual electrode configurations shown inFIGS. 4A-4D can functionally result in similar materials producedaccording to certain inventive aspects of the invention as thosematerials produced corresponding to remotely adjustable (e.g.,remote-controlled by computer or controller means) electrodeconfigurations shown in FIGS. 3A-3D. The desirability of utilizingvarious electrode configuration combinations is discussed in greaterdetail later herein.

FIGS. 5A-5E show perspective views of various desirable electrodeconfigurations for the electrode 1 shown in FIGS. 1-4 (as well as inother FIGs. and embodiments discussed later herein). The electrodeconfigurations shown in FIGS. 5A and 5E are representative of a numberof different configurations that are useful in various embodiments ofthe present invention. Criteria for appropriate electrode selection forthe electrode 1 include, but are not limited to the followingconditions: the need for a very well defined tip or point 9,composition, mechanical limitations, the ability to make shapes from thematerial comprising the electrode 1, conditioning (e.g., heat treatingor annealing) of the material comprising the electrode 1, convenience,the constituents introduced into the plasma 4, the influence upon theliquid 3, etc. In this regard, a small mass of material comprising theelectrodes 1 shown in, for example, FIGS. 1-4 may, upon creation of theadjustable plasmas 4 according to the present invention (discussed ingreater detail later herein), rise to operating temperatures where thesize and or shape of the electrode(s) 1 can be adversely affected. Inthis regard, for example, if the electrode 1 was of relatively smallmass (e.g., if the electrode(s) 1 was made of silver and weighed about0.5 gram or less) and included a very fine point as the tip 9, then itis possible that under certain sets of conditions that a fine point(e.g., a thin wire having a diameter of only a few millimeters andexposed to a few hundred to a few thousand volts; or a triangular-shapedpiece of metal) would be incapable of functioning as the electrode 1(e.g., the electrode 1 could deform or melt), absent some type ofadditional interactions (e.g., a cooling means such as a fan, etc.).Accordingly, the composition of (e.g., the material comprising) theelectrode(s) 1 may affect possible suitable electrode physical shape dueto, for example, melting points, pressure sensitivities, environmentalreactions (e.g., the local environment of the adjustable plasma 4 couldcause undesirable chemical, mechanical and/or electrochemical erosion ofthe electrode(s)), etc.

Moreover, it should be understood that in alternative preferredembodiments of the invention, well defined sharp points are not alwaysrequired for the tip 9. In this regard, the electrode 1 shown in FIG. 5Ecomprises a rounded tip 9. It should be noted that partially rounded orarc-shaped electrodes can also function as the electrode 1 because theadjustable plasma 4, which is created in the inventive embodiments shownherein (see, for example, FIGS. 1-4), can be created from roundedelectrodes or electrodes with sharper or more pointed features. Duringthe practice of the inventive techniques of the present invention, suchadjustable plasmas can be positioned or can be located along variouspoints of the electrode 1 shown in FIG. 5E. In this regard, FIG. 6 showsa variety of points “a-g” which correspond to initiating points 9 forthe plasmas 4 a-4 g which occur between the electrode 1 and the surface2 of the liquid 3. Accordingly, it should be understood that a varietyof sizes and shapes corresponding to electrode 1 can be utilized inaccordance with the teachings of the present invention. Still further,it should be noted that the tips 9, 9′ of the electrodes 1 and 5,respectively, shown in various FIGs. herein, may be shown as arelatively sharp point or a relatively blunt end. Unless specificaspects of these electrode tips 9, 9′ are discussed in greatercontextual detail, the actual shape of the electrode tip(s) 9, 9′ shownin the FIGs. should not be given great significance.

FIG. 7A shows a cross-sectional perspective view of the electrodeconfiguration corresponding to that shown in FIG. 2A (and FIG. 3A)contained within a trough member 30. This trough member 30 has a liquid3 supplied into it from the back side identified as 31 of FIG. 7A andthe flow direction “F” is out of the page toward the reader and towardthe cross-sectioned area identified as 32. The trough member 30 is shownhere as a unitary piece of one material, but could be made from aplurality of materials fitted together and, for example, fixed (e.g.,glued, mechanically attached, etc.) by any acceptable means forattaching materials to each other. Further, the trough member 30 shownhere is of a rectangular or square cross-sectional shape, but maycomprise a variety of different cross-sectional shapes (discussed ingreater detail later herein). Accordingly, the flow direction of thefluid 3 is out of the page toward the reader and the liquid 3 flows pasteach of the electrodes 1 and 5, which are, in this embodiment, locatedsubstantially in line with each other relative to the longitudinal flowdirection “F” of the fluid 3 within the trough member 30. This causesthe liquid 3 to first experience an adjustable plasma interaction withthe adjustable plasma 4 (e.g., a conditioning reaction) and subsequentlythen the conditioned fluid 3 is permitted to interact with theelectrode(s) 5. Specific desirable aspects of these electrode/liquidinteractions and electrode placement(s) are discussed in greater detailelsewhere herein.

FIG. 7B shows a cross-sectional perspective view of the electrodeconfiguration shown in FIG. 2A (as well as in FIG. 3A), however, theseelectrodes 1 and 5 are rotated on the page 90 degrees relative to theelectrodes 1 and 5 shown in FIGS. 2A and 3A. In this embodiment of theinvention, the liquid 3 contacts the adjustable plasma 4 generatedbetween the electrode 1 and the surface 2 of the liquid 3, and theelectrode 5 at substantially the same point along the longitudinal flowdirection “F” (i.e., out of the page) of the trough member 30. Thedirection of liquid 3 flow is longitudinally along the trough member 30and is out of the paper toward the reader, as in FIG. 7A. Variousdesirable aspects of this electrode configuration are discussed ingreater detail later herein.

FIG. 8A shows a cross-sectional perspective view of the same embodimentshown in FIG. 7A. In this embodiment, as in FIG. 7A, the fluid 3 firstsinteracts with the adjustable plasma 4 created between the electrode 1and the surface 2 of the liquid 3. Thereafter the plasma influenced orconditioned fluid 3, having been changed (e.g., conditioned, modified,or prepared) by the adjustable plasma 4, thereafter communicates withthe electrode(s) 5 thus permitting various electrochemical reactions tooccur, such reactions being influenced by the state (e.g., chemicalcomposition, pH, physical or crystal structure, excited state(s), etc.,of the fluid 3 (and constituents within the fluid 3)) discussed ingreater detail elsewhere herein. An alternative embodiment is shown inFIG. 8B. This embodiment essentially corresponds in general arrangementto those embodiments shown in FIGS. 3B and 4B. In this embodiment, thefluid 3 first communicates with the electrode 5, and thereafter thefluid 3 communicates with the adjustable plasma 4 created between theelectrode 1 and the surface 2 of the liquid 3.

FIG. 8C shows a cross-sectional perspective view of two electrodes 5 aand 5 b (corresponding to the embodiments shown in FIGS. 3C and 4C)wherein the longitudinal flow direction “F” of the fluid 3 contacts thefirst electrode 5 a and thereafter contacts the second electrode 5 b inthe direction “F” of fluid flow.

Likewise, FIG. 8D is a cross-sectional perspective view and correspondsto the embodiments shown in FIGS. 3D and 4D. In this embodiment, thefluid 3 communicates with a first adjustable plasma 4 a created by afirst electrode 1 a and thereafter communicates with a second adjustableplasma 4 b created between a second electrode 1 b and the surface 2 ofthe fluid 3.

FIG. 9A shows a cross-sectional perspective view and corresponds to theelectrode configuration shown in FIG. 7B (and generally to the electrodeconfiguration shown in FIGS. 3A and 4A but is rotated 90 degreesrelative thereto). All of the electrode configurations shown in FIGS. 9Aand 9D are situated such that the electrode pairs shown are locatedsubstantially at the same longitudinal point along the trough member 30,as in FIG. 7B.

Likewise, FIG. 9B corresponds generally to the electrode configurationshown in FIGS. 3B and 4B, and is rotated 90 degrees relative to theconfiguration shown in FIG. 8B.

FIG. 9C shows an electrode configuration corresponding generally toFIGS. 3C and 4C, and is rotated 90 degrees relative to the electrodeconfiguration shown in FIG. 8C.

FIG. 9D shows an electrode configuration corresponding generally toFIGS. 3D and 4D and is rotated 90 degrees relative to the electrodeconfiguration shown in FIG. 8D.

The electrode configurations shown generally in FIGS. 7, 8 and 9, allcan create different results (e.g., different conditioning effects forthe fluid 3, different pH's in the fluid 3, different sizes, shapes,and/or amounts of particulate matter found in the fluid 3, differentfunctioning of the fluid/nanoparticle combination, different zetapotentials, etc.) as a function of a variety of features including theelectrode orientation and position relative to the fluid flow direction“F”, the number of electrode pairs provided and their positioning in thetrough member 30 relative to each other. Further, the electrodecompositions, size, specific shapes, number of different types ofelectrodes provided, voltage applied, amperage applied, AC source (andAC source frequency), DC source, RF source (and RF source frequency),electrode polarity, etc., can all influence the properties of the liquid3 (and/or constituents contained in the liquid 3) as the liquid 3 flowspast these electrodes 1, 5 and hence resultant properties of thematerials (e.g., the nanoparticle solution) produced therefrom.Additionally, the liquid-containing trough member 30, in some preferredembodiments, contains a plurality of the electrode combinations shown inFIGS. 7, 8 and 9. These electrode assemblies may be all the sameconfiguration or may be a combination of various different electrodeconfigurations (discussed in greater detail elsewhere herein). Moreover,the electrode configurations may sequentially communicate with the fluid“F” or may simultaneously, or in parallel communicate with the fluid“F”. Different exemplary and preferred electrode configurations areshown in additional figures later herein and are discussed in greaterdetail later herein in conjunction with different nanoparticles andnanoparticle/solutions produced therefrom.

FIG. 10a shows a cross-sectional view of the liquid containing troughmember 30 shown in FIGS. 7, 8 and 9. This trough member 30 has across-section corresponding to that of a rectangle or a square and theelectrodes (not shown in FIG. 10A) can be suitably positioned therein.

Likewise, several additional alternative cross-sectional embodiments forthe liquid-containing trough member 30 are shown in FIGS. 10B, 10C, 10Dand 10E. The distance “S” and “S′” for the preferred embodiment shown ineach of FIGS. 10A-10E measures, for example, between about 1″ and about3″ (about 2.5 cm-7.6 cm). The distance “M” ranges from about 2″ to about4″ (about 5 cm-10 cm). The distance “R” ranges from about 1/16″-½″ toabout 3″ (about 1.6 mm-3 mm to about 76 mm). All of these embodiments(as well as additional configurations that represent alternativeembodiments are within the metes and bounds of this inventivedisclosure) can be utilized in combination with the other inventiveaspects of the invention. It should be noted that the amount of liquid 3contained within each of the liquid containing trough members 30 is afunction not only of the depth “d”, but also a function of the actualcross-section. Briefly, the amount of fluid 3 present in and around theelectrode(s) 1 and 5 can influence one or more effects of the adjustableplasma 4 upon the liquid 3 as well as the electrochemical interaction(s)of the electrode 5 with the liquid 3. These effects include not onlyadjustable plasma 4 conditioning effects (e.g., interactions of theplasma electric and magnetic fields, interactions of the electromagneticradiation of the plasma, creation of various chemical species (e.g.,Lewis acids, Bronsted-Lowry acids) within the liquid, pH changes,temperature variations of the liquid (e.g., slower liquid flow canresult in higher liquid temperatures which can also desirably influencefinal products produced), etc.) upon the liquid 3, but also theconcentration or interaction of the adjustable plasma 4 with the liquid3. Similarly, the influence of many aspects of the electrode 5 on theliquid 3 (e.g., electrochemical interactions, temperature, etc.) isalso, at least partially, a function of the amount of liquid juxtaposedto the electrode(s) 5. Further, strong electric and magnetic fieldconcentrations will also effect the interaction of the plasma 4 with theliquid 3 as well as effect the interaction of the electrode 5 with theliquid 3. Some important aspects of these important interactions arediscussed in greater detail later herein. Further, a trough member 30may comprise more than one cross-sectional shape along its entirelongitudinal length. The incorporation of multiple cross-sectionalshapes along the longitudinal length of a trough member 30 can resultin, for example, varying the field or concentration or reaction effectsbeing produced by the inventive embodiments disclosed herein (discussedin greater detail elsewhere herein). Further, a trough member 30 may notbe linear or “I-shaped”, but rather may be “Y-shaped” or “Ψ-shaped”,with each portion of the “Y” (or “Ψ”) having a different (or similar)cross-sectional shape and/or set of dimensions.

Also, the initial temperature of the liquid 3 input into the troughmember 30 can also affect a variety of properties of products producedaccording to the disclosure herein. For example, different temperaturesof the liquid 3 can affect particle size, concentration or amounts ofvarious formed constituents (e.g., transient, semi-permanent orpermanent constituents), pH, zeta potential, etc. Likewise, temperaturecontrols along at least a portion of, or substantially all of, thetrough member 30 can have similar effects.

Further, certain processing enhancers may also be added to or mixed withthe liquid(s). The processing enhancers include both solids and liquids.The processing enhancer may provide certain processing advantages and/ordesirable final product characteristics. Examples of processingenhancers may include certain acids, certain bases, salts, nitrates,etc. Processing enhancers may assist in one or more of theelectrochemical reactions disclosed herein; and/or may assist inachieving one or more desirable properties in products formed accordingto the teachings herein.

FIG. 11A shows a perspective view of one embodiment of substantially allof the trough member 30 shown in FIG. 10B including an inlet portion orinlet end 31 and an outlet portion or outlet end 32. The flow direction“F” discussed in other figures herein corresponds to a liquid enteringat or near the end 31 (e.g., utilizing an appropriate means fordelivering fluid into the trough member 30 at or near the inlet portion31) and exiting the trough member 30 through the end 32. FIG. 11B showsthe trough member 30 of FIG. 11A containing three control devices 20 a,20 b and 20 c removably attached to the trough member 30. Theinteraction and operations of the control devices 20 a, 20 b and 20 ccontaining the electrodes 1 and/or 5 are discussed in greater detaillater herein. However, in a preferred embodiment of the invention, thecontrol devices 20, can be removably attached to a top portion of thetrough member 30 so that the control devices 20 are capable of beingpositioned at different positions along the trough member 30, therebyaffecting certain processing parameters, constituents produced,reactivity of constituents produced, as well as nanoparticle(s)/fluid(s)produced therefrom.

FIG. 11C shows a perspective view of an atmosphere control device cover35′. The atmosphere control device or cover 35′ has attached thereto aplurality of control devices 20 a, 20 b and 20 c controllably attachedto electrode(s) 1 and/or 5. The cover 35′ is intended to provide theability to control the atmosphere within and/or along a substantialportion of (e.g., greater than 50% of) the longitudinal direction of thetrough member 30, such that any adjustable plasma(s) 4 created betweenany electrode(s) 1 and surface 2 of the liquid 3 can be a function ofvoltage, current, current density, polarity, etc. (as discussed in moredetail elsewhere herein) as well as a controlled atmosphere (alsodiscussed in more detail elsewhere herein).

FIG. 11D shows the apparatus of FIG. 11C including an additional supportmeans 34 for supporting the trough member 30 (e.g., on an exteriorportion thereof), as well as supporting (at least partially) the controldevices 20 (not shown in FIG. 11D). It should be understood by thereader that various details can be changed regarding, for example, thecross-sectional shapes shown for the trough member 30, atmospherecontrol(s) (e.g., the cover 35′) and external support means (e.g., thesupport means 34) which are within the metes and bounds of thisdisclosure, some of which are discussed in greater detail later herein.

FIG. 11E shows an alternative configuration for the trough member 30.Specifically, the trough member 30 is shown in perspective view and is“Y-shaped”. Specifically, the trough member 30 comprises top portions 30a and 30 b and a bottom portion 30 o. Likewise, inlets 31 a and 31 b areprovided along with outlet 32. A portion 30 d corresponds to the pointwhere 30 a and 30 b meet 30 o.

FIG. 11F shows the same “Y-shaped” trough member shown in FIG. 11E,except that the portion 30 d of FIG. 11E is now shown as a mixingsection 30 d′. In this regard, certain constituents manufactured orproduced in the liquid 3 in one or all of, for example, the portions 30a, 30 b and/or 30 c, may be desirable to be mixed together at the point30 d (or 30 d′). Such mixing may occur naturally at the intersection 30d shown in FIG. 11E (i.e., no specific or special section 30 d′ may beneeded), or may be more specifically controlled at the portion 30 d′. Itshould be understood that the portion 30 d′ could be shaped in anyeffective shape, such as square, circular, rectangular, etc., and be ofthe same or different depth relative to other portions of the troughmember 30. In this regard, the area 30 d could be a mixing zone orsubsequent reaction zone. More details of the interactions 30 d and 30d′ are discussed later herein.

FIGS. 11G and 11H show a “Ψ-shaped” trough member 30. Specifically, anew portion 30 c has been added. Other features of FIGS. 11G and 11H aresimilar to those features shown in 11E and 11F.

It should be understood that a variety of different shapes can exist forthe trough member 30, any one of which can produce desirable results asa function of a variety of design and production considerations. Forexample, one or more constituents produced in the portion(s) 30 a, 30 band/or 30 c could be transient and/or semi permanent. If suchconstituent(s) produced, for example, in portion 30 a is to be desirablyand controllably reacted with one or more constituents produced in, forexample, portion 30 b, then a final product (e.g., properties of a finalproduct) which results from such mixing could be a function of whenconstituents formed in the portions 30 a and 30 b are mixed together.For example, final properties of products made under similar sets ofconditions experienced in, for example, the portions 30 a and 30 b, ifcombined in, for example, the section 30 d (or 30 d′), could bedifferent from final properties of products made in the portions 30 aand 30 b and such products are not combined together until minutes orhours or days later. Also, the temperature of liquids entering thesection 30 d (or 30 d′) can be monitored/controlled to maximize certaindesirable properties of final products and/or minimize certainundesirable products. Still further, processing enhancers may beselectively utilized in one or more of the portions 30 a, 30 b, 30 c, 30d and/or 30 o (or at any point in the trough member 30).

FIG. 12A shows a perspective view of a local atmosphere controlapparatus 35 which functions as a means for controlling a localatmosphere around the electrode sets 1 and/or 5 so that variouslocalized gases can be utilized to, for example, control and/or effectcertain components in the adjustable plasma 4 between electrode 1 andsurface 2 of the liquid 3, as well as influence adjustableelectrochemical reactions at and/or around the electrode(s) 5. Thethrough-holes 36 and 37 shown in the atmosphere control apparatus 35 areprovided to permit external communication in and through a portion ofthe apparatus 35. In particular, the hole or inlet 37 is provided as aninlet connection for any gaseous species to be introduced to the insideof the apparatus 35. The hole 36 is provided as a communication port forthe electrodes 1 and/or 5 extending therethrough which electrodes areconnected to, for example, the control device 20 located above theapparatus 35. Gasses introduced through the inlet 37 can simply beprovided at a positive pressure relative to the local externalatmosphere and may be allowed to escape by any suitable means or pathwayincluding, but not limited to, bubbling out around the portions 39 aand/or 39 b of the apparatus 35, when such portions are caused, forexample, to be at least partially submerged beneath the surface 2 of theliquid 3 (discussed in greater detail later herein). Alternatively, asecond hole or outlet (not shown) can be provided elsewhere in theatmosphere control apparatus 35. Generally, the portions 39 a and 39 bcan break the surface 2 of the liquid 3 effectively causing the surface2 to act as part of the seal to form a localized atmosphere aroundelectrode sets 1 and/or 5. When a positive pressure of a desired gasenters through the inlet port 37, small bubbles can be caused to bubblepast, for example, the portions 39 a and/or 39 b. Alternatively, gas mayexit through an appropriate outlet in the atmosphere control apparatus35, such as through the hole 36.

FIG. 12B shows a perspective view of first atmosphere control apparatus35 a in the foreground of the trough member 30 contained within thesupport housing 34. A second atmosphere control apparatus 35 b isincluded and shows a control device 20 located thereon. “F” denotes thelongitudinal direction of flow of liquid through the trough member 30.The desirability of locally controlled atmosphere(s) (e.g., ofsubstantially the same chemical constituents, such as air or nitrogen,or substantially different chemical constituents, such as helium andnitrogen) around different electrode sets 1 and/or 5 is discussed ingreater detail later herein.

FIG. 13 shows a perspective view of an alternative atmosphere controlapparatus 38 wherein the entire trough member 30 and support means 34are contained within the atmosphere control apparatus 38. In this case,for example, gas inlet 37 (37′) can be provided along with a gasoutlet(s) 37 a (37 a′). The exact positioning of the gas inlet(s) 37(37′) and gas outlet(s) 37 a (37 a′) on the atmosphere control apparatus38 is a matter of convenience, as well as a matter of the composition ofthe atmosphere contained therein. In this regard, if the gas is heavierthan air or lighter than air, inlet and outlet locations can be adjustedaccordingly. Aspects of these factors are discussed in greater detaillater herein.

FIG. 14 shows a schematic view of the general apparatus utilized inaccordance with the teachings of some of the preferred embodiments ofthe present invention. In particular, this FIG. 14 shows a sideschematic view of the trough member 30 containing a liquid 3 therein. Onthe top of the trough member 30 rests a plurality of control devices 20a-20 d which are, in this embodiment, removably attached thereto. Thecontrol devices 20 a-20 d may of course be permanently fixed in positionwhen practicing various embodiments of the invention. The precise numberof control devices 20 (and corresponding electrode(s) 1 and/or 5 as wellas the configuration(s) of such electrodes) and the positioning orlocation of the control devices 20 (and corresponding electrodes 1and/or 5) are a function of various preferred embodiments of theinvention discussed in greater detail later herein. However, in general,an input liquid 3 (for example water or purified water) is provided to aliquid transport means 40 (e.g., a liquid pump, gravity or liquidpumping means for pumping the liquid 3) such as a peristaltic pump forpumping the liquid water 3 into the trough member 30 at a first-end 31thereof. Exactly how the liquid 3 is introduced is discussed in greaterdetail later herein. The liquid transport means 40 may include any meansfor moving liquids 3 including, but not limited to a gravity-fed orhydrostatic means, a pumping means, a regulating or valve means, etc.However, the liquid transport means 40 should be capable of reliablyand/or controllably introducing known amounts of the liquid 3 into thetrough member 30. Once the liquid 3 is provided into the trough member30, means for continually moving the liquid 3 within the trough member30 may or may not be required. However, a simple means for continuallymoving the liquid 3 includes the trough member 30 being situated on aslight angle θ (e.g., less than a degree to a few degrees for a lowviscosity fluid 3 such as water) relative to the support surface uponwhich the trough member 30 is located. For example, a difference invertical height of less than one inch between an inlet portion 31 and anoutlet portion 32, spaced apart by about 6 feet (about 1.8 meters)relative to the support surface may be all that is required, so long asthe viscosity of the liquid 3 is not too high (e.g., any viscosityaround the viscosity of water can be controlled by gravity flow oncesuch fluids are contained or located within the trough member 30). Inthis regard, FIGS. 15A and 15B show two acceptable angles θ₁ and θ₂,respectively, for trough member 30 that can process various viscosities,including low viscosity fluids such as water. The need for a greaterangle θ could be a result of processing a liquid 3 having a viscosityhigher than water; the need for the liquid 3 to transit the trough 30 ata faster rate, etc. Further, when viscosities of the liquid 3 increasesuch that gravity alone is insufficient, other phenomena such asspecific uses of hydrostatic head pressure or hydrostatic pressure canalso be utilized to achieve desirable fluid flow. Further, additionalmeans for moving the liquid 3 along the trough member 30 could also beprovided inside the trough member 30. Such means for moving the fluidinclude mechanical means such as paddles, fans, propellers, augers,etc., acoustic means such as transducers, thermal means such as heatersand/or chillers (which may have additional processing benefits), etc.,are also desirable for use with the present invention.

FIG. 14 also shows a storage tank or storage vessel 41 at the end 32 ofthe trough member 30. Such storage vessel 41 can be any acceptablevessel and/or pumping means made of one or more materials which, forexample, do not negatively interact with the liquid 3 produced withinthe trough member 30. Acceptable materials include, but are not limitedto plastics such as high density polyethylene (HDPE), glass, metal(s)(such a certain grades of stainless steel), etc. Moreover, while astorage tank 41 is shown in this embodiment, the tank 41 should beunderstood as including a means for distributing or directly bottling orpackaging the fluid 3 processed in the trough member 30.

FIGS. 16A, 16B and 16C show a perspective view of one preferredembodiment of the invention. In these FIGS. 16A, 16B and 16C, eightseparate control devices 20 a-h are shown in more detail. Such controldevices 20 can utilize one or more of the electrode configurations shownin, for example, FIGS. 8A, 8B, 8C and 8D. The precise positioning andoperation of the control devices 20 (and the corresponding electrodes 1and/or 5) are discussed in greater detail elsewhere herein. FIG. 16Bincludes use of two air distributing or air handling devices (e.g., fans342 a and 342 b). Similarly, FIG. 16C includes the use of twoalternative air distributing or air handling devices 342 c and 342 d.

FIG. 17 shows another perspective view of another embodiment of theapparatus according to the present invention wherein six control devices20 a-20 f are rotated approximately 90 degrees relative to the eightcontrol devices 20 a-20 h shown in FIGS. 16A, 16B and 16C. The preciselocation and operation of the control devices 20 and the associatedelectrodes 1 and/or 5 are discussed in greater detail elsewhere herein.

FIG. 18 shows a perspective view of the apparatus shown in FIG. 16A, butsuch apparatus is now shown as being substantially completely enclosedby an atmosphere control apparatus 38. Such apparatus 38 is a means forcontrolling the atmosphere around the trough member 30, or can be usedto isolate external and undesirable material from entering into thetrough member 30 and negatively interacting therewith. Further, the exit32 of the trough member 30 is shown as communicating with a storagevessel 41 through an exit pipe 42. Moreover, an exit 43 on the storagetank 41 is also shown. Such exit pipe 43 can be directed toward anyother suitable means for storage, packing and/or handling the liquid 3(discussed in greater detail herein).

FIGS. 19A, 19B, 19C and 19D show additional cross-sectional perspectiveviews of additional electrode configuration embodiments which can beused according to the present invention.

In particular, FIG. 19A shows two sets of electrodes 5 (i.e., 4 totalelectrodes 5 a, 5 b, 5 c and 5 d) located approximately parallel to eachother along a longitudinal direction of the trough member 30 andsubstantially perpendicular (i.e., 60°-90°) to the flow direction “F” ofthe liquid 3 through the trough member 30. In contrast, FIG. 19B showstwo sets of electrodes 5 (i.e, 5 a, 5 b, 5 c and 5 d) located adjacentto each other along the longitudinal direction of the trough member 30.

In contrast, FIG. 19C shows one set of electrodes 5 (5 a, 5 b) locatedsubstantially perpendicular to the direction of fluid flow “F” andanother set of electrodes 5 (5 c, 5 d) located substantially parallel tothe direction of the fluid flow “F”. FIG. 19D shows a mirror image ofthe electrode configuration shown in FIG. 19C. While each of FIGS. 19A,19B, 19C and 19D show only electrode(s) 5 it is clear that electrode(s)1 could be substituted for some or all of those electrode(s) 5 shown ineach of FIGS. 19A-19D, and/or intermixed therein (e.g., similar to theelectrode configurations disclosed in FIGS. 8A-8D and 9A-9D). Thesealternative electrode configurations, and some of their associatedadvantages, are discussed in greater detail herein.

FIGS. 20A-20P show a variety of cross-sectional perspective views of thevarious electrode configuration embodiments possible and usable for allthose configurations of electrodes 1 and 5 corresponding only to theembodiment shown in FIG. 19A. In particular, for example, the number ofelectrodes 1 or 5 varies in these FIGS. 20A-20P, as well as the specificlocations of such electrode(s) 1 and 5 relative to each other. Ofcourse, these electrode combinations 1 and 5 shown in FIGS. 20A-20Pcould also be configured according to each of the alternative electrodeconfigurations shown in FIGS. 19B, 19C and 19D (i.e., sixteen additionalfigures corresponding to each of FIGS. 19B, 19C and 19D) but additionalfigures have not been included herein for the sake of brevity. Specificadvantages of these electrode assemblies, and others, are disclosed ingreater detail elsewhere herein.

Each of the electrode configurations shown in FIGS. 20A-20P, dependingon the particular run conditions, can result in different productscoming from the mechanisms, apparatuses and processes of the presentinvention. A more detailed discussion of these various configurationsand advantages thereof are discussed in greater detail elsewhere herein.

FIGS. 21A, 21B, 21C and 21D show cross sectional perspective views ofadditional embodiments of the present invention. The electrodearrangements shown in these FIGS. 21A-21D are similar in arrangement tothose electrode arrangements shown in FIGS. 19A, 19B, 19C and 19D,respectively. However, in these FIGS. 21A-21D a membrane or barrierassembly 50 is also included. In these embodiments of the invention, amembrane 50 is provided as a means for separating different productsmade at or near different electrode sets so that some or all of theproducts made by the set of electrodes 1 and/or 5 on one side of themembrane 50 can be at least partially isolated, or segregated, orsubstantially completely isolated from certain products made at or nearelectrodes 1 and/or 5 on the other side of the membrane 50. Thismembrane means 50 may act as a mechanical barrier, physical barrier,mechano-physical barrier, chemical barrier, electrical barrier, etc.Accordingly, certain products made from a first set of electrodes 1and/or 5 can be at least partially, or substantially completely,isolated from certain products made from a second set of electrodes 1and/or 5. Likewise, additional serially located electrode sets can alsobe similarly situated. In other words, different membrane(s) 50 can beutilized at or near each set of electrodes 1 and/or 5 and certainproducts produced therefrom can be controlled and selectively deliveredto additional electrode sets 1 and/or 5 longitudinally downstreamtherefrom. Such membranes 50 can result in a variety of differentcompositions of the liquid 3 and/or nanoparticles or ions orconstituents present in the liquid 3 produced in the trough member 30(discussed in greater detail herein). For example, different formedcompositions in the liquid 3 can be isolated from each other.

FIG. 22A shows a perspective cross-sectional view of an electrodeassembly which corresponds to the electrode assembly 5 a, 5 b shown inFIG. 9C. This electrode assembly can also utilize a membrane 50 forchemical, physical, chemo-physical and/or mechanical separation. In thisregard, FIG. 22B shows a membrane 50 located between the electrodes 5 a,5 b. It should be understood that the electrodes 5 a, 5 b could beinterchanged with the electrodes 1 in any of the multiple configurationsshown, for example, in FIGS. 9A-9C. In the case of FIG. 22B, themembrane assembly 50 has the capability of isolating partially orsubstantially completely, some or all of the products formed atelectrode 5 a, from some or all of those products formed at electrode 5b. Accordingly, various species formed at either of the electrodes 5 aand 5 b can be controlled so that they can sequentially react withadditional electrode assembly sets 5 a, 5 b and/or combinations ofelectrode sets 5 and electrode sets 1 in the longitudinal flow direction“F” that the liquid 3 undertakes along the longitudinal length of thetrough member 30. Accordingly, by appropriate selection of membrane 50,which products located at which electrode (or subsequent or downstreamelectrode set) can be controlled, manipulated and/or adjusted. In apreferred embodiment where the polarity of the electrodes 5 a and 5 bare opposite, a variety of different products may be formed at theelectrode 5 a relative to the electrode 5 b.

FIG. 22C shows another different embodiment of the invention in across-sectional schematic view of a completely different alternativeelectrode configuration for electrodes 5 a and 5 b. In this case,electrode(s) 5 a (or of course electrode(s) 1 a) are located above amembrane 50 and electrode(s) 5 b are located below a membrane 50 (e.g.,are substantially completely submerged in the liquid 3). In this regard,the electrode(s), 5 b can comprise a plurality of electrodes or may be asingle electrode running along at least some or the entire longitudinallength of the trough member 30. In this embodiment, certain speciescreated at electrode(s) 5 above the membrane 50 can be different fromcertain species created below the membrane 50 and such species can reactdifferently along the longitudinal length of the trough member 30. Inthis regard, the membrane 50 need not run the entire length of thetrough member 30, but may be present for only a portion of such lengthand thereafter sequential assemblies of electrodes 1 and/or 5 can reactwith the products produced therefrom. It should be clear to the readerthat a variety of additional embodiments beyond those expresslymentioned here would fall within the spirit of the embodiments expresslydisclosed.

FIG. 22D shows another alternative embodiment of the invention whereby aconfiguration of electrodes 5 a (and of course electrodes 1) shown inFIG. 22C are located above a portion of a membrane 50 which extends atleast a portion along the length of a trough member 30 and a secondelectrode (or plurality of electrodes) 5 b (similar to electrode(s) 5 bin FIG. 22C) run for at least a portion of the longitudinal length alongthe bottom of the trough member 30. In this embodiment of utilizingmultiple electrodes 5 a, additional operational flexibility can beachieved. For example, by splitting the voltage and current into atleast two electrodes 5 a, the reactions at the multiple electrodes 5 acan be different from those reactions which occur at a single electrode5 a of similar size, shape and/or composition. Of course this multipleelectrode configuration can be utilized in many of the embodimentsdisclosed herein, but have not been expressly discussed for the sake ofbrevity. However, in general, multiple electrodes 1 and/or 5 (i.e.,instead of a single electrode 1 and/or 5) can add great flexibility inproducts produced according to the present invention. Details of certainof these advantages are discussed elsewhere herein.

FIG. 23A is a cross-sectional perspective view of another embodiment ofthe invention which shows a set of electrodes 5 corresponding generallyto that set of electrodes 5 shown in FIG. 19A however, the differencebetween the embodiment of FIG. 23A is a third set of electrode(s) 5 e, 5f have been provided in addition to those two sets of electrodes 5 a, 5b, 5 c and 5 d shown in FIG. 19A. Of course, the sets of electrodes 5 a,5 b, 5 c, 5 d, 5 e and 5 f can also be rotated 90 degrees so they wouldcorrespond roughly to those two sets of electrodes shown in FIG. 19B.Additional figures showing additional embodiments of those sets ofelectrode configurations have not been included here for the sake ofbrevity.

FIG. 23B shows another embodiment of the invention which also permutatesinto many additional embodiments, wherein membrane assemblies 50 a and50 b have been inserted between the three sets of electrodes 5 a,5 b-5c,5 d and 5 e,5 f. It is of course apparent that the combination ofelectrode configuration(s), number of electrode(s) and precisemembrane(s) means 50 used to achieve separation includes manyembodiments, each of which can produce different products when subjectedto the teachings of the present invention. More detailed discussion ofsuch products and operations of these embodiments are discussedelsewhere herein.

FIGS. 24A-24E; 25A-25E; and 26A-26E show cross-sectional views of avariety of membrane means 50 designs and/or locations that can beutilized according to various embodiments disclosed herein. In each ofthese embodiments, the membrane means 50 provide a means for separatingone or more products made at one or more electrode assemblies 1/5.

DETAILED DESCRIPTION OF THE DRAWINGS

FIGS. 1A, 1B and 1C show schematic cross-sectional views of a manualelectrode assembly according to the present invention.

FIGS. 2A and 2B show schematic cross-sectional views of an automaticelectrode assembly according to the present invention.

FIGS. 3A-3D show four alternative electrode configurations for theelectrodes 1 and 5 controlled by an automatic device.

FIGS. 4A-4D show four alternative electrode configurations for theelectrodes 1 and 5 which are manually controlled.

FIGS. 5A-5E show five different representative embodiments ofconfigurations for the electrode 1.

FIG. 6 shows a cross-sectional schematic view of plasmas producedutilizing one specific configuration of electrode 1.

FIGS. 7A and 7B show a cross-sectional perspective view of two electrodeassemblies utilized.

FIGS. 8A-8D show schematic perspective views of four different electrodeassemblies corresponding to those electrode assemblies shown in FIGS.3A-3D, respectively.

FIGS. 9A-9D show schematic perspective views of four different electrodeassemblies corresponding to those electrode assemblies shown in FIGS.4A-4D, respectively.

FIGS. 10A-10E show cross-sectional views of various trough members 30.

FIGS. 11A-11H show perspective views of various trough members andatmosphere control and support devices.

FIGS. 12A and 12B show various atmosphere control devices for locallycontrolling atmosphere around electrode sets 1 and/or 5.

FIG. 13 shows an atmosphere control device for controlling atmospherearound the entire trough member 30.

FIG. 14 shows a schematic cross-sectional view of a set of controldevices 20 located on a trough member 30 with a liquid 3 flowingtherethrough.

FIGS. 15A and 15B show schematic cross-sectional views of various anglesθ₁ and θ₂ for the trough member 30.

FIGS. 16A, 16B and 16C show perspective views of various control devices20 containing electrode assemblies 1 and/or 5 thereon located on top ofa trough member 30.

FIG. 17 shows a perspective view of various control devices 20containing electrode assemblies 1 and/or 5 thereon located on top of atrough member 30.

FIG. 18 shows a perspective view of various control devices 20containing electrode assemblies 1 and/or 5 thereon located on top of atrough member 30 and including an enclosure 38 which controls theenvironment around the entire device and further including a holdingtank 41.

FIGS. 19A-19D are perspective schematic views of multiple electrode setscontained within a trough member 30.

FIGS. 20A-20P show perspective views of multiple electrode sets 1/5 in16 different possible combinations.

FIGS. 21A-21D show four perspective schematic views of possibleelectrode configurations separated by a membrane 50.

FIGS. 22A-22D show a perspective schematic views of four differentelectrode combinations separated by a membrane 50.

FIGS. 23A and 23B show a perspective schematic view of three sets ofelectrodes and three sets of electrodes separated by two membranes 50 aand 50 b, respectively.

FIGS. 24A-24E show various membranes 50 located in variouscross-sections of a trough member 30.

FIGS. 25A-25E show various membranes 50 located in variouscross-sections of a trough member 30.

FIGS. 26A-26E show various membranes 50 located in variouscross-sections of a trough member 30.

FIG. 27 shows a perspective view of a control device 20.

FIGS. 28A and 28B show a perspective view of a control device 20.

FIG. 28C shows a perspective view of an electrode holder.

FIGS. 28D-28L show a variety of perspective views of different controldevices 20, with and without localized atmospheric control devices.

FIG. 29 shows a perspective view of a thermal management deviceincluding a refractory member 29 and a heat sink 28.

FIG. 30 shows a perspective view of a control device 20.

FIG. 31 shows a perspective view of a control device 20.

FIGS. 32A, 32B and 32C show AC transformer electrical wiring diagramsfor use with different embodiments of the invention.

FIG. 33A shows a schematic view of a transformer and FIGS. 33B and 33Cshow schematic representations of two sine waves in phase and out ofphase, respectively.

FIGS. 34A, 34B and 34C each show schematic views of eight electricalwiring diagrams for use with 8 sets of electrodes.

FIG. 35 shows a schematic view of an electrical wiring diagram utilizedto monitor voltages from the outputs of a secondary coil of atransformer.

FIGS. 36A, 36B and 36C show schematic views of wiring diagramsassociated with a Velleman K8056 circuit relay board.

FIG. 37A shows a bar chart of various target and actual average voltagesapplied to 16 different electrodes in an 8 electrode set used in Example1 to manufacture silver-based nanoparticles and nanoparticle solutions.

FIG. 37B-37I show actual voltages applied as a function of time for the16 different electrodes used in Example 1.

FIG. 38A shows a bar chart of various target and actual average voltagesapplied to 16 different electrodes in an 8 electrode set used in Example2 to manufacture silver-based nanoparticles and nanoparticle solutions.

FIGS. 38B-38I show actual voltages applied as a function of time for the16 different electrodes used in Example 2

FIG. 39A shows a bar chart of various target and actual average voltagesapplied to 16 different electrodes in an 8 electrode set used in Example3 to manufacture silver-based nanoparticles and nanoparticle solutions.

FIGS. 39B-39I show actual voltages applied as a function of time for 16different electrodes used in Example 3.

FIG. 40A shows a bar chart of various target and actual average voltagesapplied to 16 different electrodes in an 8 electrode set used in Example4 to manufacture zinc-based nanoparticles and nanoparticle solutions.

FIG. 40B-40I show actual voltages applied as a function of time for the16 different electrodes used in Example 4.

FIG. 41A shows a bar chart of various target and actual average voltagesapplied to 16 different electrodes in an 8 electrode set used in Example5 to manufacture copper-based nanoparticles and nanoparticle solutions.

FIGS. 41B-41I show actual voltages applied as a function of time for the16 different electrodes used in Example 5.

FIGS. 42A-E are SEM-EDS plots of the materials made in each of Examples1-5, respectively.

FIGS. 42F-O correspond to 10 different solutions GR1-GR10 made utilizingthe raw materials of Examples 1-5 (i.e., made according to Table 8 andTable 9).

FIGS. 43AA-AD-43EA-ED are SEM photomicrographs at 4 differentmagnifications in each FIG. corresponding to the raw materials ofExamples 1-5, respectively.

FIGS. 43FA-FD-430A-OD are SEM photomicrographs at 4 differentmagnifications in each FIG. corresponding to the solutions GR1-GR10disclosed in Table 8 and Table 9.

FIGS. 43PA-43PC disclose three different magnification TEMphotomicrographs of a silver constituent made corresponding to theproduction parameters used to manufacture AT031.

FIGS. 43QA-43QF disclose six different TEM photomicrographs taken atthree different magnifications of a silver constituent madecorresponding to the production parameters used to manufacture AT060.

FIGS. 43RA-43RB disclose two different TEM photomicrographs taken at twodifferent magnifications of a zinc constituent made according to theproduction parameters used to manufacture BT006.

FIGS. 43SA-43SE disclose five different TEM photomicrographs taken atthree different magnifications of a solution GR5.

FIGS. 43TA-43TJ disclose ten different TEM photomicrographs taken atthree different magnifications of a solution GR8.

FIG. 44A shows 5 UV-Vis spectra of the raw materials made according toExamples 1-5.

FIGS. 44B-44E show UV-Vis spectra of the 10 different solutions GR1-GR10shown in Table 8 and Table 9 made with the raw materials according toExamples 1-5.

FIG. 45 shows a raman spectra of each of the 10 solutions GR1-GR10 shownin Table 8 and Table 9.

FIG. 46 shows biological Bioscreen results for E. coli against the rawmaterials of Examples 1-5 and the solutions GR1-GR10 shown in Table 8and Table 9.

FIG. 47 shows biological minimum inhibitory concentration (“MIC”)results obtained with a Bioscreen device utilizing GR3 against E. coli;optimal density is plotted as a function of time.

FIG. 48 shows biological minimum inhibitory concentration (“MIC”)results obtained with a Bioscreen device utilizing GR8 against E. coli;optimal density is plotted as a function of time.

FIG. 49 shows biological results from a Bioscreen device utilizing theraw material made from Example 2 combined with various varying amountsof the raw materials made in Example 4; optimal density is plotted as afunction of time.

FIG. 50A-50D show biological results of the raw material made in Example2 obtained with a Bioscreen device with various amounts of treated wateradded thereto; optimal density is plotted as a function of time.

FIGS. 51A-51H show various cellular growth and cytotoxicity curves forsolutions GR3, GR5, GR8 and GR9 against both mini-pig kidney fibroblastcells and murine liver epithelial cells; the amount of fluorescencerelative to control (100%) cells is plotted against increasing amountsof nanoparticles.

FIGS. 52A-52F show cytotoxicity (LD₅₀) results (curves) for GR3, GR5 andGR8 against murine liver epithelial cells; the amount of fluorescencerelative to control (100%) cells is plotted against increasing amountsof nanoparticles.

FIGS. 53A-53H show LD₅₀ results (curves) for GR3, GR5, GR8 and GR9against mini-pig kidney fibroblast cells; the amount of fluorescencerelative to control (100%) cells is plotted against increasing amountsof nanoparticles.

FIG. 54 shows biological results from a Bioscreen device for theperformance of solution GR5, as formed in Table 8 and, compared to afreeze-dried and rehydrated GR5; optimal density is plotted as afunction of time.

FIGS. 55A-55C show bar charts of various target and actual averagevoltages applied to different electrodes used in Example 6 tomanufacture silver-based nanoparticles and nanoparticle solutions.

FIGS. 56A-56H show bar charts of various target and actual averagevoltages applied to different electrodes used in Example 7 tomanufacture silver-based nanoparticles and nanoparticle solutions.

FIGS. 57A-57B show Dynamic Light Scattering measurements for Example 7.

FIGS. 58A-58G are SEM photomicrographs of dried samples made accordingto Example 7.

FIGS. 59A-59C are UV-Vis Spectra taken of the liquid samples madeaccording to Example 7.

FIG. 60 shows biological Bioscreen results for the samples madeaccording to Example 7.

FIGS. 61A-61C show bar charts of various target and actual averagevoltages applied to different electrodes used in Example 8 tomanufacture silver-based nanoparticles and nanoparticle solutions.

FIGS. 62A-62C show Dynamic Light Scattering measurements for Example 8.

FIG. 63 shows biological Bioscreen results for the Example 8.

FIGS. 64A-64E show bar charts of various target and actual averagevoltages applied to different electrodes used in Example 9 tomanufacture silver-based nanoparticles and nanoparticle solutions.

FIGS. 65A-65B show a perspective view of a spectra collection apparatusused in Example 9.

FIGS. 66A-66E show spectra collected from Example 9.

FIGS. 67A-67F show representative spectra known in the art.

FIG. 68 shows biological Bioscreen results for the Example 9.

FIG. 69 show bar charts of various target and actual average voltagesapplied to different electrodes used in Example 10 to manufacturesilver-based nanoparticles and nanoparticle solutions.

FIGS. 70A-70C show spectra collected from Example 10.

FIGS. 71A-71C show spectra collected from Example 10.

FIGS. 72A-72C show various cytotoxicity curves for solutions used inExample 11 against murine liver epithelial cells; the amount offluorescence relative to control (100%) cells is plotted againstincreasing amounts of nanoparticles.

FIGS. 73A-73B show various cytotoxicity curves for solutions used inExample 11 against murine liver epithelial cells; the amount offluorescence relative to control (100%) cells is plotted againstincreasing amounts of nanoparticles.

FIGS. 74A-74B show various cytotoxicity curves for solutions used inExample 11 against murine liver epithelial cells; the amount offluorescence relative to control (100%) cells is plotted againstincreasing amounts of nanoparticles.

FIG. 75 shows a bar chart of various target and actual average voltagesapplied to different electrodes used in Example 11 to manufacturesilver-based nanoparticles and nanoparticle solutions.

FIGS. 76A-76B show various cytotoxicity curves for solutions used inExample 11 against murine liver epithelial cells; the amount offluorescence relative to control (100%) cells is plotted againstincreasing amounts of nanoparticles.

FIGS. 77A-77B show biological Bioscreen results for the Example 11.

FIGS. 78A-78B show biological Bioscreen results for the Example 12.

FIGS. 79A-79C show biological Bioscreen results for the Example 12.

FIGS. 80A-80F show Dynamic Light Scattering measurements for Example 12.

FIGS. 81A-81E show Dynamic Light Scattering measurements for Example 12.

FIGS. 82A-82F show bar charts of various target and actual voltagesapplied to six different, 8 electrode sets used in Example 13 tomanufacture both silver-based and zinc-based nanoparticles andnanoparticle solutions.

FIG. 82G shows biological Bioscreen results for the solutions discussedin Example 13.

FIGS. 83A-83C show bar charts of various target and actual voltagesapplied to three different, 8 electrode sets that were used in Example14 to manufacture gold-based nanoparticles and nanoparticle solutions.

FIG. 84A is a perspective view of a Y-shaped trough member 30 madeaccording to the invention and utilized in Example 15.

FIG. 85 is a schematic perspective view of the apparatus utilized tocollect plasma emission spectroscopy data in Example 16.

FIGS. 86A-86D show plasma irradiance using a silver electrode.

FIGS. 87A-87D show plasma irradiance using a gold electrode.

FIGS. 88A-88D show plasma irradiance using a platinum electrode.

FIG. 88E shows a plasma emission spectroscopy when two transformers areconnected in parallel.

FIGS. 89A-89D show temperature measurements and relative presence of“NO” and “OH”.

FIGS. 90A-90C, 91A-91C, and FIG. 92 show various anti-malarialactivities.

FIG. 93 shows a plot of amount of silver constituent from GR-05complexed, versus lipid concentration.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The embodiments disclosed herein relate generally to novel methods andnovel devices for the continuous manufacture of a variety ofconstituents in a liquid including nanoparticles, andnanoparticle/liquid(s) solution(s). The nanoparticles produced in thevarious liquids can comprise a variety of possible compositions, sizesand shapes, zeta potential (i.e., surface change), conglomerates,composites and/or surface morphologies which exhibit a variety of noveland interesting physical, catalytic, biocatalytic and/or biophysicalproperties. The liquid(s) used and/or created/modified during theprocess play an important role in the manufacturing of and/or thefunctioning of the nanoparticles and/or nanoparticle/liquid(s)solutions(s). The atmosphere(s) used play an important role in themanufacturing and/or functioning of the nanoparticle and/ornanoparticle/liquid(s) solution(s). The nanoparticles are caused to bepresent (e.g., created) in at least one liquid (e.g., water) by, forexample, preferably utilizing at least one adjustable plasma (e.g.,formed in one or more atmosphere(s)), which adjustable plasmacommunicates with at least a portion of a surface of the liquid. Thepower source(s) used to create the plasma(s) play(s) an important rolein the manufacturing of and/or functioning of the nanoparticles and/ornanoparticle/liquid(s) solution(s). For example, the voltage, amperage,polarity, etc., all can influence processing and/or final properties ofproduced products. Metal-based electrodes of various composition(s)and/or unique configurations are preferred for use in the formation ofthe adjustable plasma(s), but non-metallic-based electrodes can also beutilized. Utilization of at least one subsequent and/or substantiallysimultaneous adjustable electrochemical processing technique is alsopreferred. Metal-based electrodes of various composition(s) and/orunique configurations are preferred for use in the adjustableelectrochemical processing technique(s).

Adjustable Plasma Electrodes and Adjustable Electrochemical Electrodes

An important aspect of one embodiment of the invention involves thecreation of an adjustable plasma, which adjustable plasma is locatedbetween at least one electrode (or plurality of electrodes) positionedabove at least a portion of the surface of a liquid and at least aportion of the surface of the liquid itself. The surface of the liquidis in electrical communication with at least one second electrode (or aplurality of second electrodes). This configuration has certaincharacteristics similar to a dielectric barrier discharge configuration,except that the surface of the liquid is an active participant in thisconfiguration.

FIG. 1A shows a partial cross-sectional view of one embodiment of anelectrode 1 having a triangular shape located a distance “x” above thesurface 2 of a liquid 3 flowing, for example, in the direction “F”. Theelectrode 1 shown is an isosceles triangle, but may be shaped as a rightangle or equilateral triangle as well. An adjustable plasma 4 isgenerated between the tip or point 9 of the electrode 1 and the surface2 of the liquid 3 when an appropriate power source 10 is connectedbetween the point source electrode 1 and the electrode 5, whichelectrode 5 communicates with the liquid 3 (e.g., is at least partiallybelow the surface 2 (e.g., bulk surface or effective surface) of theliquid 3). It should be noted that under certain conditions the tip 9′of the electrode 5 may actually be located physically slightly above thebulk surface 2 of the liquid 3, but the liquid still communicates withthe electrode through a phenomena known as “Taylor cones” therebycreating an effective surface 2′. Taylor cones are discussed in U.S.Pat. No. 5,478,533, issued on Dec. 26, 1995 to Inculet, entitled Methodand Apparatus for Ozone Generation and Treatment of Water; the subjectmatter of which is herein expressly incorporated by reference. In thisregard, FIG. 1B shows an electrode configuration similar to that shownin FIG. 1A, except that a Taylor cone “T” is utilized to create aneffective surface 2′ to achieve electrical connection between theelectrode 5 and the surface 2 (2′) of the liquid 3. Taylor cones arereferenced in the Inculet patent as being created by an “impressedfield”. In particular, Taylor cones were first analyzed by Sir GeoffreyTaylor in the early 1960's wherein Taylor reported that the applicationof an electrical field of sufficient intensity will cause a waterdroplet to assume a conical formation. It should be noted that Taylorcones, while a function of the electric field, are also a function ofthe conductivity of the fluid. Accordingly, as conductivity changes, theshape and or intensity of a Taylor cone can also change. Accordingly,Taylor cones of various intensity can be observed near tips 9′ atelectrode(s) 5 of the present invention as a function of not only theelectric field which is generated around the electrode(s) 5, but also isa function of constituents in the liquid 3 (e.g., conductiveconstituents provided by, for example, the adjustable plasma 4) andothers. Further, electric field changes are also proportional to theamount of current applied.

The adjustable plasma region 4, created in the embodiment shown in FIG.1A, can typically have a shape corresponding to a cone-like structurefor at least a portion of the process, and in some embodiments of theinvention, can maintain such cone-like shape for substantially all ofthe process. In other embodiments, the shape of the adjustable plasmaregion 4 may be shaped more like lightning bolts. The volume, intensity,constituents (e.g., composition), activity, precise locations, etc., ofthe adjustable plasma(s) 4 will vary depending on a number of factorsincluding, but not limited to, the distance “x”, the physical and/orchemical composition of the electrode 1, the shape of the electrode 1,the location of the electrode 1 relative to other electrode(s) 1 locatedupstream from the electrode 1, the power source 10 (e.g., DC, AC,rectified AC, polarity of DC and/or rectified AC, RF, etc.), the powerapplied by the power source (e.g., the volts applied, the amps applied,frequency of pulsed DC source or AC source, etc.) the electric and/ormagnetic fields created at or near the plasma 4, the composition of thenaturally occurring or supplied gas or atmosphere between and/or aroundthe electrode 1 and the surface 2 of the liquid 3, temperature,pressure, flow rate of the liquid 3 in the direction “F”, composition ofthe liquid 3, conductivity of the liquid 3, cross-sectional area (e.g.,volume) of the liquid near and around the electrodes 1 and 5 (e.g., theamount of time the liquid 3 is permitted to interact with the adjustableplasma 4 and the intensity of such interactions), the presence ofatmosphere flow (e.g., air flow) at or near the surface 2 of the liquid3 (e.g., cooling fan(s) or atmosphere movement means provided), etc.Specifically, for example, the maximum distance “x” that can be utilizedfor the adjustable plasma 4 is where such distance “x” corresponds to,for example, the breakdown electric field “E_(c)” shown in Equation 1.In other words, achieving breakdown of the gas or atmosphere providedbetween the tip 9 of the electrode 1 and the surface 2 of the liquid 3.If the distance “x” exceeds the maximum distance required to achieveelectric breakdown (“E_(c)”), then no plasma 4 will be observed absentthe use of additional techniques or interactions. However, whenever thedistance “x” is equal to or less than the maximum distance required toachieve the formation of the adjustable plasma 4, then various physicaland/or chemical adjustments of the plasma 4 can be made. Such changeswill include, for example, diameter of the plasma 4 at the surface 2 ofthe liquid 3, intensity (e.g., brightness and/or strength and/orreactivity) of the plasma 4, the strength of the electric wind createdby the plasma 4 and blowing toward the surface 2 of the liquid 3, etc.

The composition of the electrode 1 can also play an important role inthe formation of the adjustable plasma 4. For example, a variety ofknown materials are suitable for use as the electrode(s) 1 of theembodiments disclosed herein. These materials include metals such asplatinum, gold, silver, zinc, copper, titanium, and/or alloys ormixtures thereof, etc. However, the electrode(s) 1 (and 5) can be madeof any suitable material which may comprise metal(s) (e.g., includingappropriate oxides, carbides, nitrides, carbon, silicon and mixtures orcomposites thereof, etc.). Still further, alloys of various metals arealso desirable for use with the present invention. Specifically, alloyscan provide chemical constituents of different amounts, intensitiesand/or reactivities in the adjustable plasma 4 resulting in, forexample, different properties in and/or around the plasma 4 and/ordifferent constituents being present transiently, semi-permanently orpermanently within the liquid 3. For example, different spectra can beemitted from the plasma 4 due to different constituents being excitedwithin the plasma 4, different fields can be emitted from the plasma 4,etc. Thus, the plasma 4 can be involved in the formation of a variety ofdifferent nanoparticles and/or nanoparticle/solutions and/or desirableconstituents, or intermediate(s) present in the liquid 3 required toachieve desirable end products. Still further, it is not only thechemical composition and shape factor(s) of the electrode(s) 1, 5 thatplay a role in the formation of the adjustable plasma 4, but also themanor in which any electrode(s) 1, 5 have been manufactured can alsoinfluence the performance of the electrode(s) 1, 5. In this regard, theprecise shaping technique(s) including forging, drawing and/or castingtechnique(s) utilized to from the electrode(s) 1, 5 can have aninfluence on the chemical and/or physical activity of the electrode(s)1, 5, including thermodynamic and/or kinetic and/or mechanical issues.

The creation of an adjustable plasma 4 in, for example, air above thesurface 2 of a liquid 3 (e.g., water) will, typically, produce at leastsome gaseous species such as ozone, as well as certain amounts of avariety of nitrogen-based compounds and other components. Variousexemplary materials can be produced in the adjustable plasma 4 andinclude a variety of materials that are dependent on a number of factorsincluding the atmosphere between the electrode 1 and the surface 2 ofthe liquid 3. To assist in understanding the variety of species that arepossibly present in the plasma 4 and/or in the liquid 3 (when the liquidcomprises water), reference is made to a 15 Jun. 2000 thesis byWilhelmus Frederik Laurens Maria Hoeben, entitled “Pulsed corona-induceddegradation of organic materials in water”, the subject matter of whichis expressly herein incorporated by reference. The work in theaforementioned thesis is directed primarily to the creation ofcorona-induced degradation of undesirable materials present in water,wherein such corona is referred to as a pulsed DC corona. However, manyof the chemical species referenced therein, can also be present in theadjustable plasma 4 of the embodiments disclosed herein, especially whenthe atmosphere assisting in the creation of the adjustable plasma 4comprises humid air and the liquid 3 comprises water. In this regard,many radicals, ions and meta-stable elements can be present in theadjustable plasma 4 due to the dissociation and/or ionization of any gasphase molecules or atoms present between the electrode 1 and the surface2. When humidity in air is present and such humid air is at least amajor component of the atmosphere “feeding” the adjustable plasma 4,then oxidizing species such as hydroxyl radicals, ozone, atomic oxygen,singlet oxygen and hydropereoxyl radicals can be formed. Still further,amounts of nitrogen oxides like NO_(x) and N₂O can also be formed.Accordingly, Table 1 lists some of the reactants that could be expectedto be present in the adjustable plasma 4 when the liquid 3 compriseswater and the atmosphere feeding or assisting in providing raw materialsto the adjustable plasma 4 comprises humid air.

TABLE 1 Reaction/Species Equation H₂O + e⁻ → OH + H + e⁻ dissociation 2H₂O + e⁻ → H₂O₊ + 2e⁻ ionization 3 H₂O₊ + H₂O → H₃O₊ + OH dissociation 4N₂ + e⁻ → N_(2 *) + e⁻ excitation 5 O₂ + e⁻ → O_(2 *) + e⁻ excitation 6N₂ + e⁻ → 2N + e⁻ dissociation 7 O₂ + e⁻ → 2O + e⁻ dissociation 8 N₂ +e⁻ → N₂₊ + 2e⁻ ionization 9 O₂ + e⁻ → O₂₊ + 2e⁻ ionization 10 O₂ + e⁻ →O² ⁻ attachment 11 O₂ + e⁻ → O⁻ + O dissociative attachment 12 O₂ + O →O₃ association 13 H + O₂ → HO₂ association 14 H + O₃ → HO₃ association15 N + O → NO association 16 NO + O → NO₂ association 17 N₂₊ + O²⁻ → 2NOrecombination 18 N₂ + O → N₂O association 19

An April, 1995 article, entitled “Electrolysis Processes in D.C. CoronaDischarges in Humid Air”, written by J. Lelievre, N. Dubreuil and J.-L.Brisset, and published in the J. Phys. III France 5 on pages 447-457therein (the subject matter of which is herein expressly incorporated byreference) was primarily focused on DC corona discharges and noted thataccording to the polarity of the active electrode, anions such asnitrites and nitrates, carbonates and oxygen anions were the prominentions at a negative discharge; while protons, oxygen and NO_(x) cationswere the major cationic species created in a positive discharge.Concentrations of nitrites and/or nitrates could vary with currentintensity. The article also disclosed in Table I therein (i.e., Table 2reproduced herein) a variety of species and standard electrodepotentials which are capable of being present in the DC plasmas createdtherein. Accordingly, one would expect such species as being capable ofbeing present in the adjustable plasma(s) 4 of the present inventiondepending on the specific operating conditions utilized to create theadjustable plasma(s) 4.

TABLE 2 O₃/O₂ [2.07] NO₃ ⁻/N₂ [1.24] HO₂ ⁻/OH⁻ [0.88] N₂/NH₄ ⁺ [0.27]HN₃/NH₄ ⁺ [1.96] O₂/H₂O [1.23] NO₃ ⁻/N₂O₄ [0.81] O₂/HO₂ ⁻ [−0.08]H₂O₂/H₂O [1.77] NO₃ ⁻/N₂O [1.11] NO₃ ⁻/NO₂ [0.81] CO₂/CO [−0.12] N₂O/N₂[1.77] N₂O₄/HNO₂ [1.07] NO/H₂N₂O₂ [0.71] CO₂/HCO₂H [−0.2] NO/N₂O [1.59]HNO₂/NO [0.98] O₂/H₂O₂ [0.69] N₂/N₂H₅ ⁺ [−0.23] NO⁺/NO [1.46] NO₃ ⁻/NO[0.96] NO₃ ⁻/NO₂ ⁻ [0.49] CO₂/H₂C₂O₄ [−0.49] H₃NOH⁺/ [1.42] NO₃ ⁻/HNO₂[0.94] O₂/OH⁻ [0.41] N₂H₅ ⁺ H₂O/e_(aq.) [−2.07] N₂H₅/NH₄ ⁺ [1.27]

An article published 15 Oct. 2003, entitled, “Optical and electricaldiagnostics of a non-equilibrium air plasma”, authored by XinPei Lu,Frank Leipold and Mounir Laroussi, and published in the Journal ofPhysics D: Applied Physics, on pages 2662-2666 therein (the subjectmatter of which is herein expressly incorporated by reference) focusedon the application of AC (60 Hz) high voltage (<20 kV) to a pair ofparallel electrodes separated by an air gap. One of the electrodes was ametal disc, while the other electrode was a surface of water.Spectroscopic measurements performed showed that light emission from theplasma was dominated by OH (A-X, N₂ (C-B) and N₂ ⁺ (B-X) transitions.The spectra from FIG. 4A therefrom have been reproduced herein as FIG.67A.

An article by Z. Machala, et al., entitled, “Emission spectroscopy ofatmospheric pressure plasmas for bio-medical and environmentalapplications”, published in 2007 in the Journal of MolecularSpectroscopy, discloses additional emission spectra of atmosphericpressure plasmas. The spectra from FIGS. 3 and 4 therefrom have beenreproduced as FIGS. 67B and 67C.

An article by M. Laroussi and X. Lu, entitled, “Room-temperatureatmospheric pressure plasma plume for biomedical applications”,published in 2005 in Applied Physics Letters, discloses emission spectrafrom OH, N₂, N₂ ⁺, He and O. The spectra from FIG. 4 therein has beenreproduced as FIGS. 67D, 67E and 67F.

Also known in the art is the generation of ozone by pulsed-coronadischarge over a water surface as disclosed by Petr Lukes, et al, in thearticle, “Generation of ozone by pulsed corona discharge over watersurface in hybrid gas-liquid electrical discharge reactor”, published inJ. Phys. D: Appl. Phys. 38 (2005) 409-416 (the subject matter of whichis herein expressly incorporated by reference). Lukes, et al, disclosethe formation of ozone by pulse-positive corona discharge generated in agas phase between a planar high voltage electrode (made from reticulatedvitreous carbon) and a water surface, said water having an immersedground stainless steel “point” mechanically-shaped electrode locatedwithin the water and being powered by a separate electrical source.Various desirable species are disclosed as being formed in the liquid,some of which species, depending on the specific operating conditions ofthe embodiments disclosed herein, could also be expected to be present.

Further, U.S. Pat. No. 6,749,759 issued on Jun. 15, 2004 to Denes, etal, and entitled Method for Disinfecting a Dense Fluid Medium in a DenseMedium Plasma Reactor (the subject matter of which is herein expresslyincorporated by reference), discloses a method for disinfecting a densefluid medium in a dense medium plasma reactor. Denes, et al, disclosedecontamination and disinfection of potable water for a variety ofpurposes. Denes, et al, disclose various atmospheric pressure plasmaenvironments, as well as gas phase discharges, pulsed high voltagedischarges, etc. Denes, et al, use a first electrode comprising a firstconductive material immersed within the dense fluid medium and a secondelectrode comprising a second conductive material, also immersed withinthe dense fluid medium. Denes, et al then apply an electric potentialbetween the first and second electrodes to create a discharge zonebetween the electrodes to produce reactive species in the dense fluidmedium.

All of the constituents discussed above, if present, can be at leastpartially (or substantially completely) managed, controlled, adjusted,maximized, minimized, eliminated, etc., as a function of such speciesbeing helpful or harmful to the resultant nanoparticles and/ornanoparticle/solutions produced, and then may need to be controlled by avariety of different techniques (discussed in more detail later herein).As shown in FIG. 1A, the adjustable plasma 4 contacts the actual surface2 of the liquid 3. In this embodiment of the invention, material (e.g.,metal) from the electrode 1 may comprise a portion of the adjustableplasma 4 and may be caused, for example, to be “sputtered” onto and/orinto the liquid (e.g., water). Accordingly, when metal(s) are used asthe electrode(s) 1, elementary metal(s), metal ions, Lewis acids,Bronsted-Lowry acids, metal oxides, metal nitrides, metal hydrides,metal hydrates, metal carbides, and/or mixtures thereof etc., can befound in the liquid (e.g., for at least a portion of the process),depending upon the particular set of operating conditions associatedwith the adjustable plasma 4 (as well as other operating conditions).

Additionally, by controlling the temperature of the liquid 3 in contactwith the adjustable plasma 4, the amount(s) of certain constituentspresent in the liquid 3 (e.g., for at least a portion of the processand/or in final products produced) can be maximized or minimized. Forexample, if a gaseous species such as ozone created in the adjustableplasma 4 was desired to be present in relatively larger quantities, thetemperature of the liquid 3 could be reduced (e.g., by a chilling orrefrigerating procedure) to permit the liquid 3 to contain more of thegaseous species. In contrast, if a relatively lesser amount of aparticular gaseous species was desired to be present in the liquid 3,the temperature of the liquid 3 could be increased (e.g., by thermalheating, microwave heating, etc.) to contain less of the gaseousspecies. Similarly, often species in the adjustable plasma 4 beingpresent in the liquid 3 could be adjusting/controlling the temperatureof the liquid 3 to increase or decrease the amount of such speciespresent in the liquid 3.

Further, certain processing enhancers may also be added to or mixed withthe liquid(s). The processing enhancers include both solids and liquids.The processing enhancer may provide certain processing advantages and/ordesirable final product characteristics. Examples of processingenhancers may include certain acids, certain bases, salts, nitrates,etc. Processing enhancers may assist in one or more of theelectrochemical reactions disclosed herein; and/or may assist inachieving one or more desirable properties in products formed accordingto the teachings herein.

Further, depending on, for example, electric, magnetic and/orelectromagnetic field strength, polarity, etc., in and around the liquid3, as well as the volume of liquid 3 present (e.g., a function of, forexample, the cross-sectional size and shape of the trough member 30and/or flow rate of the liquid 3) discussed in greater detail elsewhereherein), the physical and chemical construction of the electrode(s) 1and 5, atmosphere (naturally occurring or supplied), liquid 3composition, greater or lesser amounts of electrode(s) materials(s)(e.g., metal(s) or derivatives of metals) may be found in the liquid 3.Additional important information is disclosed in copending patentapplication entitled Methods for Controlling Crystal Growth,Crystallization, Structures and Phases in Materials and Systems; whichwas filed on Mar. 21, 2003, and was published by the World IntellectualProperty Organization under publication number WO 03/089692 on Oct. 30,2003 and the U.S. National Phase application, which was filed on Jun. 6,2005, and was published by the United States Patent and Trademark Officeunder publication number 20060037177 on Feb. 23, 2006 (the inventors ofeach being Bentley J. Blum, Juliana H. J. Brooks and Mark G. Mortenson).The subject matter of both applications is herein expressly incorporatedby reference. These published applications disclose (among other things)that the influence of, for example, electric fields, magnetic fields,electromagnetic energy, etc., have proven to be very important in theformation and/or control of various structures in a variety of solids,liquids, gases and/or plasmas. Such disclosed effects are also relevantin the embodiments disclosed herein. Further, the observation of extremevariations of, for example, pH in and around electrodes having apotential applied thereto (and current flow therethrough) also controlsreaction products and/or reaction rates. Thus, a complex set ofreactions are likely to be occurring at each electrode 1, 5 andelectrode assemblies or electrode sets (e.g., 1, 5; 1, 1; 5, 5; etc.).

In certain situations, the material(s) (e.g., metal(s), metal ion(s),metal composite(s) or constituents (e.g., Lewis acids, Bronsted-Lowryacids, etc.) and/or inorganics found in the liquid 3 (e.g., afterprocessing thereof) may have very desirable effects, in which caserelatively large amounts of such material(s) will be desirable; whereasin other cases, certain materials found in the liquid (e.g., undesirableby-products) may have undesirable effects, and thus minimal amounts ofsuch material(s) may be desired in the final product. Further, thestructure/composition of the liquid 3 per se may also be beneficially ornegatively affected by the processing conditions of the presentinvention. Accordingly, electrode composition can play an important rolein the ultimate material(s) (e.g., nanoparticles and/ornanoparticle/solutions) that are formed according to the embodimentsdisclosed herein. As discussed above herein, the atmosphere involvedwith the reactions occurring at the electrode(s) 1 (and 5) plays animportant role. However, electrode composition also plays an importantrole in that the electrodes 1 and 5 themselves can become part of, atleast partially, intermediate and/or final products formed.Alternatively, electrodes may have a substantial role in the finalproducts. In other words, the composition of the electrodes may be foundin large part in the final products of the invention or may compriseonly a small chemical part of products produced according to theembodiments disclosed herein. In this regard, when electrode(s) 1, 5 arefound to be somewhat reactive according to the process conditions of thevarious embodiments disclosed herein, it can be expected that ionsand/or physical particles (e.g., metal-based particles of single ormultiple crystals) from the electrodes can become part of a finalproduct. Such ions and/or physical components may be present as apredominant part of a particle in a final product, may exist for only aportion of the process, or may be part of a core in a core-shellarrangement present in a final product. Further, the core-shellarrangement need not include complete shells. For example, partialshells and/or surface irregularities or specific desirable surfaceshapes on a formed nanoparticle can have large influence on the ultimateperformance of such nanoparticles in their intended use.

Also, the nature and/or amount of the surface change (i.e., positive ornegative) on formed nanoparticles can also have a large influence on thebehavior and/or effects of the nanoparticle/solution of final productsand their relative performance.

Such surface changes are commonly referred to as “zeta potential”. Ingeneral, the larger the zeta potential (either positive or negative),the greater the stability of the nanoparticles in the solution. However,by controlling the nature and/or amount of the surface changes of formednanoparticles the performance of such nanoparticle solutions in avariety of systems can be controlled (discussed in greater detail laterherein). It should be clear to an artisan of ordinary skill that slightadjustments of chemical composition, reactive atmospheres, powerintensities, temperatures, etc., can cause a variety of differentchemical compounds (both semi-permanent and transient) nanoparticles(and nanoparticle components) to be formed, as well as differentnanoparticle/solutions (e.g., including modifying the structures of theliquid 3 (such as water) per se).

Still further, the electrode(s) 1 and 5 may be of similar chemicalcomposition or completely different chemical compositions and/or made bysimilar or completely different forming processes in order to achievevarious compositions of ions, compounds, and/or physical particles inliquid and/or structures of liquids per se and/or specific effects fromfinal resultant products. For example, it may be desirable thatelectrode pairs, shown in the various embodiments herein, be of the sameor substantially similar composition, or it may be desirable for theelectrode pairs, shown in the various embodiments herein, to be ofdifferent chemical composition(s). Different chemical compositions mayresult in, of course, different constituents being present for possiblereaction in the various plasma and/or electrochemical embodimentsdisclosed herein. Further, a single electrode 1 or 5 (or electrode pair)can be made of at least two different metals, such that components ofeach of the metals, under the process conditions of the disclosedembodiments, can interact with each other, as well as with otherconstituents in the plasma(s) 4 and or liquid(s) 3, fields, etc.,present in, for example, the plasma 4 and/or the liquid 3.

Further, the distance between the electrode(s) 1 and 5; or 1 and 1(e.g., see FIGS. 3D, 4D, 8D and 9D) or 5 and 5 (e.g., see FIGS. 3C, 4C,8C and 9C) is one important aspect of the invention. In general, thelocation of the smallest distance “y” between the closest portions ofthe electrode(s) used in the present invention should be greater thanthe distance “x” in order to prevent an undesirable arc or formation ofan unwanted corona or plasma occurring between the electrode (e.g., theelectrode(s) 1 and the electrode(s) 5). Various electrode design(s),electrode location(s) and electrode interaction(s) are discussed in moredetail in the Examples section herein.

The power applied through the power source 10 may be any suitable powerwhich creates a desirable adjustable plasma 4 and desirable adjustableelectrochemical reaction under all of the process conditions of thepresent invention. In one preferred mode of the invention, analternating current from a step-up transformer (discussed in the “PowerSources” section and the “Examples” section) is utilized. In otherpreferred embodiments of the invention, polarity of an alternatingcurrent power source is modified by diode bridges to result in apositive electrode 1 and a negative electrode 5; as well as a positiveelectrode 5 and a negative electrode 1. In general, the combination ofelectrode(s) components 1 and 5, physical size and shape of theelectrode(s) 1 and 5, electrode manufacturing process, mass ofelectrodes 1 and/or 5, the distance “x” between the tip 9 of electrode 1above the surface 2 of the liquid 3, the composition of the gas betweenthe electrode tip 9 and the surface 2, the flow rate and/or flowdirection “F” of the liquid 3, compositions of the liquid 3,conductivity of the liquid 3, temperature of the liquid 3, voltage,amperage, polarity of the electrodes, etc., all contribute to thedesign, and thus power requirements (e.g., breakdown electric field or“E_(c)” of Equation 1) all influence the formation of a controlled oradjustable plasma 4 between the surface 2 of the liquid 3 and theelectrode tip 9.

In further reference to the configurations shown in FIGS. 1A and 1B,electrode holders 6 a and 6 b are capable of being lowered and raised(and thus the electrodes are capable of being lowered and raised) in andthrough an insulating member 8 (shown in cross-section). The embodimentshown here are male/female screw threads. However, the electrode holders6 a and 6 b can be configured in any suitable means which allows theelectrode holders 6 a and 6 b to be raised and/or lowered reliably. Suchmeans include pressure fits between the insulating member 8 and theelectrode holders 6 a and 6 b, notches, mechanical hanging means,movable annulus rings, etc. In other words, any means for reliablyfixing the height of the electrode holders 6 a and 6 b should beconsidered as being within the metes and bounds of the embodimentsdisclosed herein.

For example, FIG. 1C shows another embodiment for raising and loweringthe electrodes 1, 5. In this embodiment, electrical insulating portions7 a and 7 b of each electrode are held in place by a pressure fitexisting between the friction mechanism 13 a, 13 b and 13 c, and theportions 7 a and 7 b. The friction mechanism 13 a, 13 b and 13 c couldbe made of, for example, spring steel, flexible rubber, etc., so long assufficient contact is maintained thereafter.

The portions 6 a and 6 b can be covered by, for example, additionalelectrical insulating portions 7 a and 7 b. The electrical insulatingportions 7 a and 7 b can be any suitable electrically insulatingmaterial (e.g., plastic, rubber, fibrous materials, etc.) which preventundesirable currents, voltage, arcing, etc., that could occur when anindividual interfaces with the electrode holders 6 a and 6 b (e.g.,attempts to adjust the height of the electrodes). Moreover, rather thanthe electrical insulating portion 7 a and 7 b simply being a cover overthe electrode holder 6 a and 6 b, such insulating portions 7 a and 7 bcan be substantially completely made of an electrical insulatingmaterial. In this regard, a longitudinal interface may exist between theelectrical insulating portions 7 a/7 b and the electrode holder 6 a/6 brespectively (e.g., the electrode holder 6 a/6 b may be made of acompletely different material than the insulating portion 7 a/7 b andmechanically or chemically (e.g., adhesively) attached thereto.

Likewise, the insulating member 8 can be made of any suitable materialwhich prevents undesirable electrical events (e.g., arcing, melting,etc.) from occurring, as well as any material which is structurally andenvironmentally suitable for practicing the present invention. Typicalmaterials include structural plastics such as polycarbonate plexiglass(poly (methyl methacrylate), polystyrene, acrylics, and the like.Certain criteria for selecting structural plastics and the like include,but are not limited to, the ability to maintain shape and/or rigidity,while experiencing the electrical, temperature and environmentalconditions of the process. Preferred materials include acrylics,plexiglass, and other polymer materials of known chemical, electricaland electrical resistance as well as relatively high mechanicalstiffness. In this regard, desirable thicknesses for the member 8 are onthe order of about 1/16″-¾″ (1.6 mm-19.1 mm).

The power source 10 can be connected in any convenient electrical mannerto the electrodes 1 and 5. For example, wires 11 a and 11 b can belocated within at least a portion of the electrode holders 6 a, 6 b witha primary goal being achieving electrical connections between theportions 11 a, 11 b and thus the electrodes 1, 5. Specific details ofpreferred electrical connections are discussed elsewhere herein.

FIG. 2A shows another schematic view of a preferred embodiment of theinvention, wherein an inventive control device 20 is connected to theelectrodes 1 and 5, such that the control device 20 remotely (e.g., uponcommand from another device) raises and/or lowers the electrodes 1, 5relative to the surface 2 of the liquid 3. The inventive control device20 is discussed in more detail later herein. In this preferredembodiment of the invention, the electrodes 1 and 5 can be, for example,remotely lowered and controlled, and can also be monitored andcontrolled by a suitable controller or computer (not shown in FIG. 2A)containing a software program (discussed in detail later herein). Inthis regard, FIG. 2B shows an electrode configuration similar to thatshown in FIG. 2A, except that a Taylor cone “T” is utilized forelectrical connection between the electrode 5 and the effective surface2′ of the liquid 3. Accordingly, the embodiments shown in FIGS. 1A, 1Band 1C should be considered to be a manually controlled apparatus foruse with the teachings of the present invention, whereas the embodimentsshown in FIGS. 2A and 2B should be considered to include an automaticapparatus or assembly which can remotely raise and lower the electrodes1 and 5 in response to appropriate commands. Further, the FIG. 2A andFIG. 2B preferred embodiments of the invention can also employ computermonitoring and computer control of the distance “x” of the tips 9 of theelectrode(s) 1 (and tips 9′ of the electrodes 5) away from the surface 2(discussed in greater detail later herein). Thus, the appropriatecommands for raising and/or lowering the electrodes 1 and 5 can comefrom an individual operator and/or a suitable control device such as acontroller or a computer (not shown in FIG. 2A).

FIG. 3A corresponds in large part to FIGS. 2A and 2B, however, FIGS. 3B,3C and 3D show various alternative electrode configurations that can beutilized in connection with certain preferred embodiments of theinvention. FIG. 3B shows essentially a mirror image electrode assemblyfrom that electrode assembly shown in FIG. 3A. In particular, as shownin FIG. 3B, with regard to the direction “F” corresponding to the flowdirection of the liquid 3 in FIG. 3B, the electrode 5 is the firstelectrode which communicates with the fluid 3 when flowing in thelongitudinal direction “F” and the electrode 1 subsequently contacts thefluid 3 already modified by the electrode 5. FIG. 3C shows twoelectrodes 5 a and 5 b located within the fluid 3. This particularelectrode configuration corresponds to another preferred embodiment ofthe invention. In particular, any of the electrode configurations shownin FIGS. 3A-3D, can be used in combination with each other. For example,the electrode configuration (i.e., the electrode set) shown in FIG. 3Acan be the first electrode set or configuration that a liquid 3 flowingin the direction “F” encounters. Thereafter, the liquid 3 couldencounter a second electrode set or configuration 3 a; or alternatively,the liquid 3 could encounter a second electrode set or configuration 3b; or, alternatively, the liquid 3 flowing in the direction “F” couldencounter a second electrode set like that shown in FIG. 3C; or,alternatively, the liquid 3 flowing in the direction “F” could encountera second electrode set similar to that shown in FIG. 3D. Alternatively,if the first electrode configuration or electrode set encountered by aliquid 3 flowing in the direction “F” is the electrode configurationshown in FIG. 3A, a second electrode set or configuration could besimilar to that shown in FIG. 3C and a third electrode set or electrodeconfiguration that a liquid 3 flowing in the direction “F” couldencounter could thereafter be any of the electrode configurations shownin FIGS. 3A-3D. Alternatively, a first electrode set or configurationthat a liquid 3 flowing in the direction “F” could encounter could bethat electrode configuration shown in FIG. 3D; and thereafter a secondelectrode set or configuration that a liquid 3 flowing in the direction“F” could encounter could be that electrode configuration shown in FIG.3C; and thereafter any of the electrode sets or configurations shown inFIGS. 3A-3D could comprise the configuration for a third set ofelectrodes. Still further, a first electrode configuration that a liquid3 flowing in the direction “F” may encounter could be the electrodeconfiguration shown in FIG. 3A; and a second electrode configurationcould be an electrode configuration also shown in FIG. 3A; andthereafter a plurality of electrode configurations similar to that shownin FIG. 3C could be utilized. In another embodiment, all of theelectrode configurations could be similar to that of FIG. 3A. In thisregard, a variety of electrode configurations (including number ofelectrode sets utilized) are possible and each electrode configurationresults in either very different resultant constituents in the liquid 3(e.g., nanoparticle or nanoparticle/solution mixtures) or only slightlydifferent constituents (e.g., nanoparticle/nanoparticle solutionmixtures) all of which may exhibit different properties (e.g., differentchemical properties, different reactive properties, different catalyticproperties, etc.). In order to determine the desired number of electrodesets and desired electrode configurations and more particularly adesirable sequence of electrode sets, many factors need to be consideredincluding all of those discussed herein such as electrode composition,plasma composition (and atmosphere composition) and intensity, powersource, electrode polarity, voltage, amperage, liquid flow rate, liquidcomposition, liquid conductivity, cross-section (and volume of fluidtreated), magnetic, electromagnetic and/or electric fields created inand around each of the electrodes in each electrode assembly, whetherany field intensifiers are included, additional desired processing steps(e.g., electromagnetic radiation treatment) the desired amount ofcertain constituents in an intermediate product and in the finalproduct, etc. Some specific examples of electrode assembly combinationsare included in the “Examples” section later herein. However, it shouldbe understood that the embodiments of the present invention allow aplethora of electrode combinations and numbers of electrode sets, any ofwhich can result in very desirable nanoparticles/solutions for differentspecific chemical, catalytic, biological and/or physical applications.

With regard to the adjustable plasmas 4 shown in FIGS. 3A, 3B and 3D,the distance “x” (or in FIG. 3D “xa” and “xb”) are one means forcontrolling certain aspects of the adjustable plasma 4. In this regard,if nothing else in FIG. 3A, 3B or 3D was changed except for the distance“x”, then different intensity adjustable plasmas 4 can be achieved. Inother words, one adjustment means for adjusting plasma 4 (e.g., theintensity) is adjusting the distance “x” between the tip 9 of theelectrode 1 and the surface 2 of the fluid 3. Changing of such distancecan be accomplished up to a maximum distance “x” where the combinedvoltage and amperage are no longer are sufficient to cause a breakdownof the atmosphere between the tip 9 and the surface 2 according toEquation 1. Accordingly, the maximum preferable distances “x” are justslightly within or below the range where “E_(c)” breakdown of theatmosphere begins to occur. Alternatively, the minimum distances “x” arethose distances where an adjustable plasma 4 forms in contrast to theother phenomena discussed earlier herein where a Taylor cone forms. Inthis regard, if the distance “x” becomes so small that the liquid 3tends to wick or contact the tip 9 of the electrode 1, then no visuallyobservable plasma will be formed. Accordingly, the minimum and maximumdistances “x” are a function of all of the factors discussed elsewhereherein including amount of power applied to the system, composition ofthe atmosphere, composition (e.g., electrical conductivity) of theliquid, etc. Further, intensity changes in the plasma(s) 4 may alsoresult in certain species becoming active, relative to other processingconditions. This may result in, for example, different spectralemissions from the plasma(s) 4 as well as changes in amplitude ofvarious spectral lines in the plasma(s) 4. Also, such species may havegreater and/or lesser effects on the liquid 3 as a function of thetemperature of the liquid 3. Certain preferred distances “x” for avariety of electrode configurations and compositions are discussed inthe “Examples” section later herein.

Still further, with regard to FIG. 3D, the distances “xa” and “xb” canbe about the same or can be substantially different. In this regard, inone preferred embodiment of the invention, for a liquid 3 flowing in thedirection “F”, it is desirable that the adjustable plasma 4 a havedifferent properties than the adjustable plasma 4 b. In this regard, itis possible that different atmospheres can be provided so that thecomposition of the plasmas 4 a and 4 b are different from each other,and it is also possible that the height “xa” and “xb” are different fromeach other. In the case of differing heights, the intensity or powerassociated with each of the plasmas 4 a and 4 b can be different (e.g.,different voltages can be achieved). In this regard, because theelectrodes 1 a and 1 b are electrically connected, the total amount ofpower in the system will remain substantially constant, and the amountof power thus provided to one electrode 1 a or 1 b will increase at theexpense of the power decreasing in the other electrode 1 a or 1 b.Accordingly, this is another inventive embodiment for controllingconstituents and/or intensity and/or presence or absence of spectralpeaks in the plasmas 4 a and 4 b and thus adjusting their interactionswith the liquid 3 flowing in the direction “F”.

Likewise, a set of manually controllable electrode configurations areshown in FIGS. 4A, 4B, 4C and 4D which are shown in a partialcross-sectional view. Specifically, FIG. 4A corresponds substantially toFIG. 1A. Moreover, FIG. 4B corresponds in electrode configuration to theelectrode configuration shown in FIG. 3B; FIG. 4C corresponds to FIG. 3Cand FIG. 4D corresponds to FIG. 3D. In essence, the manual electrodeconfigurations shown in FIGS. 4A-4D can functionally result in similarmaterials produced according to the inventive aspects of the inventionas those materials and compositions produced corresponding to remotelyadjustable (e.g., remote-controlled) electrode configurations shown inFIGS. 3A-3D. However, one or more operators will be required to adjustmanually those electrode configurations. Still further, in certainembodiments, a combination of manually controlled and remotelycontrolled electrode(s) and/or electrode sets may be desirable.

FIGS. 5A-5E show perspective views of various desirable electrodeconfigurations for the electrode(s) 1 shown in the figures herein. Theelectrode configurations shown in FIGS. 5A-5E are representative of anumber of different configurations that are useful in variousembodiments of the present invention. Criteria for appropriate electrodeselection for the electrode 1 include, but are not limited to thefollowing conditions: the need for a very well defined tip or point 9,composition of the electrode 1, mechanical limitations encountered whenforming the compositions comprising the electrode 1 into various shapes,shape making capabilities associated with forging techniques, wiredrawing and/or casting processes utilized to make shapes, convenience,etc. In this regard, a small mass of material comprising the electrodes1 shown in, for example, FIGS. 1-4 may, upon creation of the adjustableplasmas 4 according to the present invention, rise to operationtemperatures where the size and or shape of the electrode(s) 1 can beadversely affected. The use of the phrase “small mass” should beunderstood as being a relative description of an amount of material usedin an electrode 1, which will vary in amount as a function ofcomposition, forming means, process conditions experienced in the troughmember 30, etc. For example, if an electrode 1, comprises silver, and isshaped similar to the electrode shown in FIG. 5A, in certain preferredembodiments shown in the Examples section herein, its mass would beabout 0.5 grams-8 grams with a preferred mass of about 1 gram-3 grams;whereas if an electrode 1, comprises copper, and is shaped similar tothe electrode shown in FIG. 5A, in certain preferred embodiments shownin the Examples section herein, its mass would be about 0.5 grams-6grams with a preferred mass of about 1 gram-3 grams; whereas if anelectrode 1, comprises zinc, and is shaped similar to the electrodeshown in FIG. 5A, in certain preferred embodiments shown in the Examplessection herein, its mass would be about 0.5 grams-4 grams with apreferred mass of about 1 gram-3 grams; whereas if the electrode 1comprises gold and is shaped similar to the electrode shown in FIG. 5E,its mass would be about 1.5 grams-20 grams with a preferred mass ofabout 5 grams-10 grams. In this regard, for example, when the electrode1 comprises a relatively small mass, then certain power limitations maybe associated with utilizing a small mass electrode 1. In this regard,if a large amount of power is applied to a relatively small mass andsuch power results in the creation of an adjustable plasma 4, then alarge amount of thermal energy can be concentrated in the small masselectrode 1. If the small mass electrode 1 has a very high meltingpoint, then such electrode may be capable of functioning as an electrode1 in the present invention. However, if the electrode 1 is made of acomposition which has a relatively low melting point (e.g., such assilver, aluminum, or the like) then under some (but not all) embodimentsof the invention, the thermal energy transferred to the small masselectrode 1 could cause one or more undesirable effects includingmelting, cracking, or disintegration of the small mass electrode 1.Accordingly, one choice for utilizing lower melting point metals is touse larger masses of such metals so that thermal energy can bedissipated throughout such larger mass. Alternatively, if a small masselectrode 1 with low melting point is desired, then some type of coolingmeans could be required. Such cooling means include, for example, simplefans blowing ambient or applied atmosphere past the electrode 1, orother such means as appropriate. However, one potential undesirableaspect for providing a cooling fan juxtaposed a small mass electrode 1is that the atmosphere involved with forming the adjustable plasma 4could be adversely affected. For example, the plasma could be found tomove or gyrate undesirably if, for example, the atmosphere flow aroundor between the tip 9 and the surface 2 of the liquid 3 was vigorous.Accordingly, the composition of (e.g., the material comprising) theelectrode(s) 1 may affect possible suitable electrode physical shape(s)due to, for example, melting points, pressure sensitivities,environmental reactions (e.g., the local environment of the adjustableplasma 4 could cause chemical, mechanical and/or electrochemical erosionof the electrode(s)), etc.

Moreover, it should be understood that in alternative preferredembodiments of the invention, well defined sharp points for the tip 9are not always required. In this regard, the electrode 1 shown in FIG.5E (which is a perspective drawing) comprises a rounded point. It shouldbe noted that partially rounded or arc-shaped electrodes can alsofunction as the electrode 1 because often times the adjustable plasma 4,can be positioned or be located along various points of the electrode 1shown in FIG. 5E. In this regard, FIG. 6 shows a variety of points “a-g”which correspond to initiating points 9 for the plasmas 4 a-4 g whichoccur between the electrode 1 and the surface 2 of the liquid 3. Forexample, in practicing certain preferred embodiments of the invention,the precise location of the adjustable plasma 4 will vary as a functionof time. Specifically, a first plasma 4 d may be formed at the point don the tip 9 of the electrode 1. Thereafter, the exact location of theplasma contact point on the tip 9 may change to, for example, any of theother points 4 a-4 g. It should be noted that the schematic shown inFIG. 6 is greatly enlarged relative to the actual arrangement in theinventive embodiments, in order to make the point that the tip 9 on theelectrode 1 may permit a variety of precise points a-g as being theinitiating or contact point on tip 9 on the electrode 1. Essentially,the location of the adjustable plasma 4 can vary in position as afunction of time and can be governed by electric breakdown of theatmosphere (according to Equation 1 herein) located between theelectrode 1 and the surface 2 of the liquid 3. Further, while theplasmas 4 a-4 g are represented as being cone-shaped, it should beunderstood that the plasmas 4, formed in connection with any of theelectrodes 1, shown in FIGS. 5A-5E, may comprise shapes other than conesfor a portion of, or substantially all of, the process conditions. Forexample, shapes best described as lightning bolts or glowing cylinderscan also be present. Further, the colors emitted by such plasmas 4(e.g., in the visible spectrum) can vary wildly from reddish in color,bluish in color, yellow in color, orangish in color, violet in color,white in color, etc., which colors are a function of atmosphere present,voltage, amperage, electrode composition, liquid composition ortemperature, etc.

Accordingly, it should be understood that a variety of sizes and shapescorresponding to electrode 1 can be utilized in accordance with theteachings of the present invention. Still further, it should be notedthat the tips 9 of the electrodes 1 shown in various figures herein maybe shown as a relatively sharp point or a relatively blunt end. Unlessspecific aspects of these electrode tips are discussed in greatercontextual detail, the actual shape of the electrode tip(s) shown in theFIGs. should not be given great significance.

FIG. 7A shows a cross-sectional perspective view of the electrodeconfiguration corresponding to that shown in FIG. 2A (and FIG. 3A)contained within a trough member 30. This trough member 30 has a liquid3 supplied into it from the back side 31 of FIG. 7A and the flowdirection “F” is out of the page toward the reader and toward thecross-sectional area identified as 32. The trough member 30 is shownhere as a unitary of piece of one material, but could be made from aplurality of materials fitted together and, for example, fixed (e.g.,glued, mechanically attached, etc.) by any acceptable means forattaching materials to each other. Further, the trough member 30 shownhere is of a rectangular or square cross-sectional shape, but maycomprise a variety of different cross-sectional shapes. Further, thetrough member 30 does not necessarily need to be made of a singlecross-sectional shape, but in another preferred embodiment herein,comprises a plurality of different cross-sectional shapes to accommodatedifferent desirable processing steps. In a first preferred embodimentthe cross-sectional shape is roughly the same throughout thelongitudinal dimension of the trough member 30 but the size dimensionsof the cross-sectional shape change in coordination with differentplasma and/or electrochemical reactions. Further, more than twocross-sectional shapes can be utilized in a unitary trough member 30.The advantages of the different cross-sectional shapes include, but arenot limited to, different power, electric field, magnetic field,electromagnetic interactions, electrochemical, effects, differentchemical reactions in different portions, different temperatures, etc.,which are capable of being achieved in different longitudinal portionsof the same unitary trough member 30. Still further, some of thedifferent cross-sectional shapes can be utilized in conjunction with,for example, different atmospheres being provided locally or globallysuch that at least one of the adjustable plasma(s) 4 and/or at least oneof the electrochemical reactions occurring at the electrode(s) 5 are afunction of different possible atmospheres and/or atmosphericconcentrations of constituents therein. Further, the amount or intensityof applied and/or created fields can be enhanced by, for example,cross-sectional shape, as well as by providing, for example, variousfield concentrators at, near, adjacent to or juxtaposed against variouselectrode sets or electrode configurations to enhance or diminish one ormore reactions occurring there. Accordingly, the cross-sectional shapeof the trough member 30 can influence both liquid 3 interactions withthe electrode(s) as well as adjustable plasma 4 interactions with theliquid 3.

Still further, it should be understood that a trough member need not beonly linear or “I-shaped”, but rather, may be shaped like a “Y” or likea “Ψ”, each portion of which may have similar or dissimilarcross-sections. One reason for a “Y” or “Ψ”-shaped trough member 30 isthat two different sets of processing conditions can exist in the twoupper portions of the “Y”-shaped trough member 30. For example, one ormore constituents produced in the portion(s) 30 a, 30 b and/or 30 ccould be transient and/or semi permanent. If such constituent(s)produced, for example, in portion 30 a is to be desirably andcontrollably reacted with one or more constituents produced in, forexample, portion 30 b, then a final product (e.g., properties of a finalproduct) which results from such mixing could be a function of whenconstituents formed in the portions 30 a and 30 b are mixed together.For example, final properties of products made under similar sets ofconditions experienced in, for example, the portions 30 a and 30 b, ifcombined in, for example, the section 30 d (or 30 d′), could bedifferent from final properties of products made in the portions 30 aand 30 b and such products are not combined together until minutes orhours or days later. Also, the temperature of liquids entering thesection 30 d (or 30 d′) can be monitored/controlled to maximize certaindesirable properties of final products and/or minimize certainundesirable products. Further, a third set of processing conditions canexist in the bottom portion of the “Y”-shaped trough member 30. Thus,two different fluids 3, of different compositions and/or differentreactants, could be brought together into the bottom portion of the“Y”-shaped trough member 30 and processed together to from a largevariety of final products some of which are not achievable by separatelymanufacturing certain solutions and later mixing such solutionstogether. Still further, processing enhancers may be selectivelyutilized in one or more of the portions 30 a, 30 b, 30 c, 30 d and/or 30o (or at any point in the trough member 30).

FIG. 11E shows an alternative configuration for the trough member 30.Specifically, the trough member 30 is shown in perspective view and is“Y-shaped”. Specifically, the trough member 30 comprises top portions 30a and 30 b and a bottom portion 30 o. Likewise, inlets 31 a and 31 b areprovided along with outlet 32. A portion 30 d corresponds to the pointwhere 30 a and 30 b meet 30 o.

FIG. 11F shows the same “Y-shaped” trough member shown in FIG. 11E,except that the portion 30 d of FIG. 11E is now shown as a mixingsection 30 d′. In this regard, certain constituents manufactured orproduced in the liquid 3 in one or all of, for example, the portions 30a, 30 b and/or 30 c, may be desirable to be mixed together at the point30 d (or 30 d′). Such mixing may occur naturally at the intersection 30d shown in FIG. 11E (i.e., no specific or special section 30 d′ may beneeded), or may be more specifically controlled at the portion 30 d′. Itshould be understood that the portion 30 d′ could be shaped in anyeffective shape, such as square, circular, rectangular, etc., and be ofthe same or different depth relative to other portions of the troughmember 30. In this regard, the area 30 d could be a mixing zone orsubsequent reaction zone and may be a function of a variety of designand/or production considerations.

FIGS. 11G and 11H show a “Ψ-shaped” trough member 30. Specifically, anew portion 30 c has been added. Other features of FIGS. 11G and 11H aresimilar to those features shown in 11E and 11F.

It should be understood that a variety of different shapes can exist forthe trough member 30, any one of which can produce desirable results.

Again with regard to FIG. 7A, the flow direction of the liquid 3 is outof the page toward the reader and the liquid 3 flows past each of theelectrode(s) 1 and 5, sequentially, which are, in this embodiment,located substantially in line with each other relative to thelongitudinal flow direction “F” of the liquid 3 within the trough member30 (e.g., their arrangement is parallel to each other and thelongitudinal dimensions of the trough member 30). This causes the liquid3 to first experience an adjustable plasma 4 interaction with the liquid3 (e.g., a conditioning reaction) and subsequently then the conditionedliquid 3 can thereafter interact with the electrode 5. As discussedearlier herein, a variety of constituents can be expected to be presentin the adjustable plasma 4 and at least a portion of such constituentsor components (e.g., chemical, physical and/or fluid components) willinteract with at least of the portion of the liquid 3 and change theliquid 3. Accordingly, subsequent reactions (e.g., electrochemical) canoccur at electrode(s) 5 after such components or constituents oralternative liquid structure(s) have been caused to be present in theliquid 3. Thus, it should be apparent from the disclosure of the variousembodiments herein, that the type, amount and activity of constituentsor components in the adjustable plasma 4 are a function of a variety ofconditions associated with practicing the preferred embodiments of thepresent invention. Such constituents (whether transient or semipermanent), once present and/or having at least partially modified theliquid 3, can favorably influence subsequent reactions along thelongitudinal direction of the trough member 30 as the liquid 3 flows inthe direction “F” therethrough. By adjusting the types of reactions(e.g., electrode assemblies and reactions associated therewith) andsequentially providing additional similar or different electrode sets orassemblies (such as those shown in FIGS. 3A-3D) a variety of compounds,nanoparticles and nanoparticle/solution(s) can be achieved. For example,nanoparticles may experience growth (e.g., apparent or actual) withinthe liquid 3 as constituents within the liquid 3 pass by and interactwith various electrode sets (e.g., 5, 5) along the longitudinal lengthof the trough member 30 (discussed in greater detail in the Examplessection). Such growth, observed at, for example, electrode sets 5, 5,seems to be greatly accelerated when the liquid 3 has previously beencontacted with an electrode set 1, 5 and/or 1, 1 and/or 5, 1 and suchgrowth can also be influenced by the temperature of the liquid 3.Depending on the particular final uses of the liquid 3 producedaccording to the invention, certain nanoparticles, some constituents inthe liquid 3, etc., could be considered to be very desirable; whereasother constituents could be considered to be undesirable. However, dueto the versatility of the electrode design, number of electrode sets,electrode set configuration, fluid composition, fluid temperature,processing conditions at each electrode in each electrode assembly orset, sequencing of different electrode assemblies or sets along thelongitudinal direction of the trough member 30, shape of the troughmember 30, cross-sectional size and shape of the trough member 30, allsuch conditions can contribute to more or less of desirable orundesirable constituents or components (transient or semi-permanent)present in the liquid 3 and/or differing structures of the liquid per seduring at least a portion of the processes disclosed herein.

FIG. 7B shows a cross-sectional perspective view of the electrodeconfiguration shown in FIG. 2A (as well as in FIG. 3A), however, theseelectrodes 1 and 5 are rotated on the page 90 degrees relative to theelectrodes 1 and 5 shown in FIGS. 2A and 3A. In this embodiment of theinvention, the liquid 3 contacts the adjustable plasma 4 generatedbetween the electrode 1 and the surface 2 of the liquid 3, and theelectrode 5 at substantially the same point along the longitudinal flowdirection “F” (i.e., out of the page) of the trough member 30. Thedirection of liquid 3 flow is longitudinally along the trough member 30and is out of the paper toward the reader, as in FIG. 7A. Accordingly,as discussed immediately above herein, it becomes clear that theelectrode assembly shown in FIG. 7B can be utilized with one or more ofthe electrode assemblies or sets discussed above herein as well as laterherein. For example, one use for the assembly shown in FIG. 7B is thatwhen the constituents created in the adjustable plasma 4 (or resultantproducts in the liquid 3) flow downstream from the contact point withthe surface 2 of the liquid 3, a variety of subsequent processing stepscan occur. For example, the distance “y” between the electrode 1 and theelectrode 5 (as shown, for example, in FIG. 7B) is limited to certainminimum distances as well as certain maximum distances. The minimumdistance “y” is that distance where the distance slightly exceeds theelectric breakdown “E_(c)” of the atmosphere provided between theclosest points between the electrodes 1 and 5. Whereas the maximumdistance “y” corresponds to the distance at a maximum which at leastsome conductivity of the fluid permits there to be an electricalconnection from the power source 10 into and through each of theelectrode(s) 1 and 5 as well as through the liquid 3. The maximumdistance “y” will vary as a function of, for example, constituentswithin the liquid 3 (e.g., conductivity of the liquid 3), temperature ofthe liquid 3, etc. Accordingly, some of those highly energizedconstituents comprising the adjustable plasma 4 could be very reactiveand could create compounds (reactive or otherwise) within the liquid 3and a subsequent processing step could be enhanced by the presence ofsuch constituents or such very reactive components or constituents couldbecome less reactive as a function of, for example, time. Moreover,certain desirable or undesirable reactions could be minimized ormaximized by locations and/or processing conditions associated withadditional electrode sets downstream from that electrode set shown in,for example, FIG. 7B. Further, some of the components in the adjustableplasma 4 could be increased or decreased in presence in the liquid 3 bycontrolling the temperature of the liquid 3.

FIG. 8A shows a cross-sectional perspective view of the same embodimentshown in FIG. 7A. In this embodiment, as in the embodiment shown in FIG.7A, the fluid 3 firsts interacts with the adjustable plasma 4 createdbetween the electrode 1 and the surface 2 of the liquid 3. Thereafterthe plasma influenced or conditioned fluid 3, having been changed (e.g.,conditioned, or modified or prepared) by the adjustable plasma 4,thereafter communicates with the electrode 5 thus permitting variouselectrochemical reactions to occur, such reactions being influenced bythe state (e.g., chemical composition, physical or crystal structure,excited state(s), temperature, etc., of the fluid 3 (and constituents orcomponents in the fluid 3)). An alternative embodiment is shown in FIG.8B. This embodiment essentially corresponds in general to thoseembodiments shown in FIGS. 3B and 4B. In this embodiment, the fluid 3first communicates with the electrode 5, and thereafter the fluid 3communicates with the adjustable plasma 4 created between the electrode1 and the surface 2 of the liquid 3.

FIG. 8C shows a cross-sectional perspective view of two electrodes 5 aand 5 b (corresponding to the embodiments shown in FIGS. 3C and 4C)wherein the longitudinal flow direction “F” of the fluid 3 contacts thefirst electrode 5 a and thereafter contacts the second electrode 5 b inthe direction “F” of fluid flow.

Likewise, FIG. 8D is a cross-sectional perspective view and correspondsto the embodiments shown in FIGS. 3D and 4D. In this embodiment, thefluid 3 communicates with a first adjustable plasma 4 a created by afirst electrode 1 a and thereafter communicates with a second adjustableplasma 4 b created between a second electrode 1 b and the surface 2 ofthe fluid 3.

Accordingly, it should be clear from the disclosed embodiments that thevarious electrode configurations or sets shown in FIGS. 8A-8D can beused alone or in combination with each other in a variety of differentconfigurations. A number of factors direct choices for which electrodeconfigurations are best to be used to achieve various desirable results.As well, the number of such electrode configurations and the location ofsuch electrode configurations relative to each other all influenceresultant constituents within the liquid 3, zeta potential,nanoparticles and/or nanoparticle/liquid solutions resulting therefrom.Some specific examples of electrode configuration dependency areincluded in the “Examples” section herein. However, it should beapparent to the reader a variety of differing products and desirableset-ups are possible according to the teachings (both expressly andinherently) present herein, which differing set-ups can result in verydifferent products (discussed further in the “Examples” section herein).

FIG. 9A shows a cross-sectional perspective view and corresponds to theelectrode configuration shown in FIG. 7B (and generally to the electrodeconfiguration shown in FIGS. 3A and 4A but is rotated 90 degreesrelative thereto). All of the electrode configurations shown in FIGS.9A-9D are situated such that the electrode pairs shown are locatedsubstantially at the same longitudinal point along the trough member 30,as in FIG. 7B.

Likewise, FIG. 9B corresponds generally to the electrode configurationshown in FIGS. 3B and 4B, and is rotated 90 degrees relative to theconfiguration shown in FIG. 8B.

FIG. 9C shows an electrode configuration corresponding generally toFIGS. 3C and 4C, and is rotated 90 degrees relative to the electrodeconfiguration shown in FIG. 8C.

FIG. 9D shows an electrode configuration corresponding generally toFIGS. 3D and 4D and is rotated 90 degrees relative to the electrodeconfiguration shown in FIG. 8D.

As discussed herein, the electrode configurations or sets showngenerally in FIGS. 7, 8 and 9, all can create different results (e.g.,different sizes, shapes, amounts, compounds, constituents, functioningof nanoparticles present in a liquid, different liquid structures,different pH's, different zeta potentials, etc.) as a function of theirorientation and position relative to the fluid flow direction “F” andrelative to their positioning in the trough member 30, relative to eachother. Further, the electrode number, compositions, size, specificshapes, voltages applied, amperages applied, frequencies applied, fieldscreated, distance between electrodes in each electrode set, distancebetween electrode sets, etc., can all influence the properties of theliquid 3 as it flows past these electrodes and hence resultantproperties of the materials (e.g., the constituents in the fluid 3, thenanoparticles and/or the nanoparticle/solution) produced therefrom.Additionally, the liquid-containing trough member 30, in some preferredembodiments, contains a plurality of the electrode combinations shown inFIGS. 7, 8 and 9. These electrode assemblies may be all the same or maybe a combination of various different electrode configurations.Moreover, the electrode configurations may sequentially communicate withthe fluid “F” or may simultaneously, or in parallel communicate with thefluid “F”. Different exemplary electrode configurations are shown inadditional figures later herein and are discussed in greater detaillater herein (e.g., in the “Examples” section) in conjunction withdifferent constituents produced in the liquid 3, nanoparticles and/ordifferent nanoparticle/solutions produced therefrom.

FIG. 10A shows a cross-sectional view of the liquid containing troughmember 30 shown in FIGS. 7, 8 and 9. This trough member 30 has across-section corresponding to that of a rectangle or a square and theelectrodes (not shown in FIG. 10A) can be suitably positioned therein.

Likewise, several additional alternative cross-sectional embodiments forthe liquid-containing trough member 30 are shown in FIGS. 10B, 10C, 10Dand 10E. The distance “S” and “S′” for the preferred embodiments shownin each of FIGS. 10A-10E measures, for example, between about 1″ andabout 3″ (about 2.5 cm-7.6 cm). The distance “M” ranges from about 2″ toabout 4″ (about 5 cm-10 cm). The distance “R” ranges from about 1/16″-½″to about 3″ (about 1.6 mm-13 mm to about 76 mm). All of theseembodiments (as well as additional configurations that representalternative embodiments are within the metes and bounds of thisinventive disclosure) can be utilized in combination with the otherinventive aspects of the invention. It should be noted that the amountof liquid 3 contained within each of the liquid containing troughmembers 30 is a function not only of the depth “d”, but also a functionof the actual cross-section. Briefly, the amount or volume and/ortemperature of liquid 3 present in and around the electrode(s) 1 and 5can influence one or more effect(s) (e.g., fluid or concentrationeffects including field concentration effects) of the adjustable plasma4 upon the liquid 3 as well as one or more chemical or electrochemicalinteraction(s) of the electrode 5 with the liquid 3. These effectsinclude not only adjustable plasma 4 conditioning effects (e.g.,interactions of the plasma electric and magnetic fields, interactions ofthe electromagnetic radiation of the plasma, creation of variouschemical species (e.g., Lewis acids, Bronsted-Lowry acids, etc.) withinthe liquid, pH changes, zeta potentials, etc.) upon the liquid 3, butalso the concentration or interaction of the adjustable plasma 4 withthe liquid 3 and electrochemical interactions of the electrode 5 withthe liquid 3. Different effects are possible due to, for example, theactual volume of liquid present around a longitudinal portion of eachelectrode assembly 1 and/or 5. In other words, for a given length alongthe longitudinal direction of the trough member 30, different amounts orvolume of liquid 3 will be present as a function of cross-sectionalshape. As a specific example, reference is made to FIGS. 10A and 10C. Inthe case of FIG. 10A, the rectangular shape shown therein has a topportion about the same distance apart as the top portion shown in FIG.10C. However, the amount of fluid along the same given longitudinalamount (i.e., into the page) will be significantly different in each ofFIGS. 10A and 10C.

Similarly, the influence of many aspects of the electrode 5 on theliquid 3 (e.g., electrochemical interactions) is also, at leastpartially, a function of the amount of fluid juxtaposed to theelectrode(s) 5, the temperature of the fluid 3, etc., as discussedimmediately above herein.

Further, electric and magnetic field concentrations can alsosignificantly affect the interaction of the plasma 4 with the liquid 3,as well as affect the interactions of the electrode(s) 5 with the liquid3. For example, without wishing to be bound by any particular theory orexplanation, when the liquid 3 comprises water, a variety of electricfield, magnetic field and/or electromagnetic field influences can occur.Specifically, water is a known dipolar molecule which can be at leastpartially aligned by an electric field. Having partial alignment ofwater molecules with an electric field can, for example, causepreviously existing hydrogen bonding and bonding angles to be orientedat an angle different than prior to electric field exposure, causedifferent vibrational activity, or such bonds may actually be broken.Such changing in water structure can result in the water having adifferent (e.g., higher) reactivity. Further, the presence of electricand magnetic fields can have opposite effects on ordering or structuringof water and/or nanoparticles present in the water. It is possible thatunstructured or small structured water having relatively fewer hydrogenbonds relative to, for example, very structured water, can result in amore reactive (e.g., chemically more reactive) environment. This is incontrast to open or higher hydrogen-bonded networks which can slowreactions due to, for example, increased viscosity, reduceddiffusivities and a smaller activity of water molecules. Accordingly,factors which apparently reduce hydrogen bonding and hydrogen bondstrength (e.g, electric fields) and/or increase vibrational activity,can encourage reactivity and kinetics of various reactions.

Further, electromagnetic radiation can also have direct and indirecteffects on water and it is possible that the electromagnetic radiationper se (e.g., that radiation emitted from the plasma 4), rather than theindividual electric or magnetic fields alone can have such effects, asdisclosed in the aforementioned published patent application entitledMethods for Controlling Crystal Growth, Crystallization, Structures andPhases in Materials and Systems which has been incorporated by referenceherein. Different spectra associated with different plasmas 4 arediscussed in the “Examples” section herein.

Further, by passing an electric current through the electrode(s) 1and/or 5 disclosed herein, the voltages present on, for example, theelectrode(s) 5 can have an orientation effect (i.e., temporary,semi-permanent or longer) on the water molecules. The presence of otherconstituents (i.e., charged species) in the water may enhance suchorientation effects. Such orientation effects may cause, for example,hydrogen bond breakage and localized density changes (i.e., decreases).Further, electric fields are also known to lower the dielectric constantof water due to the changing (e.g., reduction of) the hydrogen bondingnetwork. Such changing of networks should change the solubilityproperties of water and may assist in the concentration or dissolutionof a variety of gases and/or constituents or reactive species in theliquid 3 (e.g., water) within the trough member 30. Still further, it ispossible that the changing or breaking of hydrogen bonds fromapplication of electromagnetic radiation (and/or electric and magneticfields) can perturb gas/liquid interfaces and result in more reactivespecies. Still further, changes in hydrogen bonding can affect carbondioxide hydration resulting in, among other things, pH changes. Thus,when localized pH changes occur around, for example, at least one ormore of the electrode(s) 5 (or electrode(s) 1), many of the possiblereactants (discussed elsewhere herein) will react differently withthemselves and/or the atmosphere and/or the adjustable plasma(s) 4 aswell as the electrode(s) 1 and/or 5, per se. The presence of Lewis acidsand/or Bronsted-Lowry acids, can also greatly influence reactions.

Further, a trough member 30 may comprise more than one cross-sectionalshapes along its entire longitudinal length. The incorporation ofmultiple cross-sectional shapes along the longitudinal length of atrough member 30 can result in, for example, a varying field orconcentration or reaction effects being produced by the inventiveembodiments disclosed herein. Additionally, various modifications can beadded at points along the longitudinal length of the trough member 30which can enhance and/or diminish various of the field effects discussedabove herein. In this regard, compositions of materials in and/or aroundthe trough (e.g., metals located outside or within at least a portion ofthe trough member 30) can act as concentrators or enhancers of variousof the fields present in and around the electrode(s) 1 and/or 5.Additionally, applications of externally-applied fields (e.g., electric,magnetic, electromagnetic, etc.) and/or the placement of certainreactive materials within the trough member 30 (e.g., at least partiallycontacting a portion of the liquid 3 flowing thereby) can also resultin: (1) a gathering, collecting or filtering of undesirable species; or(2) placement of desirable species onto, for example, at least a portionof an outer surface of nanoparticles already formed upstream therefrom.Further, it should be understood that a trough member 30 may not belinear or “I-shaped”, but rather may be “Y-shaped” or “Ψ-shaped”, witheach portion of the “Y” or “Ψ” having a different (or similar)cross-section. One reason for a “Y” or “Ψ-shaped” trough member 30 isthat two (or more) different sets of processing conditions can exist inthe two (or more) upper portions of the “Y-shaped” or “Ψ-shaped” troughmember 30. Additionally, the “Y-shaped” or “Ψ-shaped” trough members 30permit certain transient or semi-permanent constituents present in theliquids 3 to interact; in contrast to separately manufactured liquids 3in “I-shaped” trough members and mixing such liquids 3 together at apoint in time which is minutes, hours or days after the formation of theliquids 3. Further, another additional set of processing conditions canexist in the bottom portion of the “Y-shaped” or “Ψ-shaped” troughmembers 30. Thus, different fluids 3, of different compositions and/ordifferent reactants (e.g., containing certain transient orsemi-permanent species), could be brought together into the bottomportion of the “Y-shaped” or “Ψ-shaped” trough members 30 and processedtogether to from a large variety of final products.

FIG. 11A shows a perspective view of one embodiment of substantially allof the trough member 30 shown in FIG. 10B including an inlet portion orinlet end 31 and an outlet portion or outlet end 32. The flow direction“F” discussed in other figures herein corresponds to a liquid enteringat or near the end 31 (e.g., utilizing an appropriate means fordelivering fluid into the trough member 30 at or near the inlet portion31) and exiting the trough member 30 through the outlet end 32.Additionally, while a single inlet end 31 is shown in FIG. 11A, multipleinlet(s) 31 could be present near that shown in FIG. 11A, or could belocated at various positions along the longitudinal length of the troughmember 30 (e.g., immediately upstream from one or more of the electrodesets positioned along the trough member 30). Thus, the plurality ofinlet(s) 31 can permit the introduction of more than one liquid 3 (ordifferent temperatures of a similar liquid 3) at a first longitudinalend 31 thereof; or the introduction of multiple liquids 3 (or multipletemperatures of similar liquids 3) at the longitudinal end 31; theintroduction of different liquids 3 (or different temperatures ofsimilar liquids 3) at different positions along the longitudinal lengthof the trough member 30; and/or one or more processing enhancers atdifferent positions along the longitudinal length of the trough member30.

FIG. 11B shows the trough member 30 of FIG. 11A containing three controldevices 20 removably attached to a top portion of the trough member 30.The interaction and operations of the control devices 20 containing theelectrodes 1 and/or 5 are discussed in greater detail later herein.

FIG. 11C shows a perspective view of the trough member 30 incorporatingan atmosphere control device cover 35′. The atmosphere control device orcover 35′ has attached thereto a plurality of control devices 20 (inFIG. 11C, three control devices 20 a, 20 b and 20 c are shown)containing electrode(s) 1 and/or 5. The cover 35′ is intended to providethe ability to control the atmosphere within and/or along a substantialportion of (e.g., greater than 50% of) the longitudinal direction of thetrough member 30, such that any adjustable plasma(s) 4 created at anyelectrode(s) 1 can be a function of voltage, current, current density,etc., as well as any controlled atmosphere provided. The atmospherecontrol device 35′ can be constructed such that one or more electrodesets can be contained within. For example, a localized atmosphere can becreated between the end portions 39 a and 39 b along substantially allor a portion of the longitudinal length of the trough member 30 and atop portion of the atmosphere control device 35′. An atmosphere can becaused to flow into at least one inlet port (not shown) incorporatedinto the atmosphere control device 35′ and can exit through at least oneoutlet port (not shown), or be permitted to enter/exit along or near,for example, the portions 39 a and 39 b. In this regard, so long as apositive pressure is provided to an interior portion of the atmospherecontrol device 35′ (i.e., positive relative to an external atmosphere)then any such gas can be caused to bubble out around the portions 39 aand/or 39 b. Further, depending on, for example, if one portion of 39 aor 39 b is higher relative to the other, an internal atmosphere may alsobe appropriately controlled. A variety of atmospheres suitable for usewithin the atmosphere control device 35′ include conventionally regardednon-reactive atmospheres like noble gases (e.g., argon or helium) orconventionally regarded reactive atmospheres like, for example, oxygen,nitrogen, ozone, controlled air, etc. The precise composition of theatmosphere within the atmosphere control device 35′ is a function ofdesired processing techniques and/or desired constituents to be presentin the plasma 4 and/or the liquid 3, desired nanoparticles/compositenanoparticles and/or desired nanoparticles/solutions.

FIG. 11D shows the apparatus of FIG. 11C including an additional supportmeans 34 for supporting the trough member 30 (e.g., on an exteriorportion thereof), as well as supporting (at least partially) the controldevices 20 (not shown in this FIG. 11C). It should be understood thatvarious details can be changed regarding, for example, thecross-sectional shapes shown for the trough member 30, atmospherecontrol(s) (e.g., the atmosphere control device 35′) and externalsupport means (e.g., the support means 34) all of which should beconsidered to be within the metes and bounds of this inventivedisclosure. The material(s) comprising the additional support means 34for supporting the trough member 30 can be any material which isconvenient, structurally sound and non-reactive under the processconditions practiced for the present inventive disclosure. Acceptablematerials include polyvinyls, acrylics, plexiglass, structural plastics,nylons, teflons, etc., as discussed elsewhere herein.

FIG. 11E shows an alternative configuration for the trough member 30.Specifically, the trough member 30 is shown in perspective view and is“Y-shaped”. Specifically, the trough member 30 comprises top portions 30a and 30 b and a bottom portion 30 o. Likewise, inlets 31 a and 31 b areprovided along with outlet 32. A portion 30 d corresponds to the pointwhere 30 a and 30 b meet 30 o.

FIG. 11F shows the same “Y-shaped” trough member shown in FIG. 11E,except that the portion 30 d of FIG. 11E is now shown as a mixingsection 30 d′. In this regard, certain constituents manufactured orproduced in the liquid 3 in one or all of, for example, the portions 30a, 30 b and/or 30 c, may be desirable to be mixed together at the point30 d (or 30 d′). Such mixing may occur naturally at the intersection 30d shown in FIG. 11E (i.e., no specific or special section 30 d′ may beneeded), or may be more specifically controlled at the portion 30 d′. Itshould be understood that the portion 30 d′ could be shaped in anyeffective shape, such as square, circular, rectangular, etc., and be ofthe same or different depth relative to other portions of the troughmember 30. In this regard, the area 30 d could be a mixing zone orsubsequent reaction zone. Further, it should be understood that liquids3 having substantially similar or substantially different composition(s)can be produced at substantially similar or substantially differenttemperatures along the portions 30 a, 30 b and/or 30 c. Also, thetemperature of the liquid(s) input into each of the portions 30 a, 30 band/or 30 c an also be controlled to desirably affect processingconditions within these portions 30 a, 30 b and/or 30 c.

FIGS. 11G and 11H show a “Ψ-shaped” trough member 30. Specifically, anew portion 30 c has been added. Other features of FIGS. 11G and 11H aresimilar to those features shown in 11E and 11F.

It should be understood that a variety of different shapes can exist forthe trough member 30, any one of which can produce desirable results.

FIG. 12A shows a perspective view of a local atmosphere controlapparatus 35 which functions as a means for controlling a localatmosphere around at least one electrode set 1 and/or 5 so that variouslocalized gases can be utilized to, for example, control and/or effectcertain parameters of the adjustable plasma 4 between electrode 1 andsurface 2 of the liquid 3, as well as influence certain constituentswithin the liquid 3 and/or adjustable electrochemical reactions atand/or around the electrode(s) 5. The through-holes 36 and 37 shown inthe atmosphere control apparatus 35 are provided to permit externalcommunication in and through a portion of the apparatus 35. Inparticular, the hole or inlet 37 is provided as an inlet connection forany gaseous species to be introduced to the inside of the apparatus 35.The hole 36 is provided as a communication port for the electrodes 1and/or 5 extending therethrough which electrodes are connected to, forexample, the control device 20 above the apparatus 35. Gasses introducedthrough the inlet 37 can simply be provided at a positive pressurerelative to the local external atmosphere and may be allowed to escapeby any suitable means or pathway including, but not limited to, bubblingout around the portions 39 a and/or 39 b of the apparatus 35, when suchportions are caused, for example, to be at least partially submergedbeneath the surface 2 of the liquid 3. Generally, the portions 39 a and39 b can break the surface 2 of the liquid 3 effectively causing thesurface 2 to act as part of the seal to form a localized atmospherearound electrode sets 1 and/or 5. When a positive pressure of a desiredgas enters through the inlet port 37, small bubbles can be caused tobubble past, for example, the portions 39 a and/or 39 b. Additionally,the precise location of the inlet 37 can also be a function of the gasflowing therethrough. Specifically, if a gas providing at least aportion of a localized atmosphere is heavier than air, then an inletportion above the surface 2 of the liquid 3 should be adequate. However,it should be understood that the inlet 37 could also be located in, forexample, 39 a or 39 b and could be bubbled through the liquid 3 andtrapped within an interior portion of the localized atmosphere controlapparatus 35. Accordingly, precise locations of inlets and/or outlets inthe atmosphere control device 35 are a function of several factors.

FIG. 12B shows a perspective view of first atmospheric control apparatus35 a in the foreground of the trough member 30 contained within thesupport housing 34. A second atmospheric control apparatus 35 b isincluded and shows a control device 20 located thereon. “F” denotes thelongitudinal direction of flow of liquid 3 through the trough member 30.A plurality of atmospheric control apparatuses 35 a, 35 b (as well as 35c, 35 d, etc. not shown in drawings) can be utilized instead of a singleatmosphere control device such as that shown in FIG. 11C. The reason fora plurality of localized atmosphere control devices 35 a-35 x is thatdifferent atmospheres can be present around each electrode assembly, ifdesired. Accordingly, specific aspects of the adjustable plasma(s) 4 aswell as specific constituents present in the liquid 3 and specificaspects of the adjustable electrochemical reactions occurring at, forexample, electrode(s) 5, will be a function of, among other things, thelocalized atmosphere. Accordingly, the use of one or more localizedatmosphere control device 35 a provides tremendous flexibility in theformation of desired constituents, nanoparticles, and nanoparticlesolution mixtures.

FIG. 13 shows a perspective view of an alternative atmosphere controlapparatus 38 wherein the entire trough member 30 and support means 34are contained within the atmospheric control apparatus 38. In this case,for example, one or more gas inlets 37, 37′ can be provided along withone or more gas outlets 37 a, 37 a′. The exact positioning of the gasinlets 37, 37′ and gas outlets 37 a, 37 a′ on the atmospheric controlapparatus 38 is a matter of convenience, as well as a matter of thecomposition of the atmosphere. In this regard, if, for example, theatmosphere provided is heavier than air or lighter than air, inlet andoutlet locations can be adjusted accordingly. As discussed elsewhereherein, the gas inlet and gas outlet portions could be provided above orbelow the surface 2 of the liquid 3. Of course, when gas inlet portionsare provided below the surface 2 of the liquid 3 (not specifically shownin this FIG.), it should be understood that bubbled (e.g., nanobubblesand/or microbubbles) of the gas inserted through the gas inlet 37 couldbe incorporated into the liquid 3, for at least a portion of theprocessing time. Such bubbles could be desirable reaction constituents(i.e., reactive with) the liquid 3 and/or constituents within the liquid3 and/or the electrode(s) 5, etc. Accordingly, the flexibility ofintroducing a localized atmosphere below the surface 2 of the liquid 3can provide additional processing control and/or processingenhancements.

FIG. 14 shows a schematic view of the general apparatus utilized inaccordance with the teachings of some of the preferred embodiments ofthe present invention. In particular, this FIG. 14 shows a sideschematic view of the trough member 30 containing a liquid 3 therein. Onthe top of the trough member 30 rests a plurality of control devices 20a-20 d (i.e., four of which are shown) which are, in this embodiment,removably attached thereto. The control devices 20 may of course bepermanently fixed in position when practicing various embodiments of theinvention. The precise number of control devices 20 (and correspondingelectrode(s) 1 and/or 5 as well as the configuration(s) of suchelectrodes) and the positioning or location of the control devices 20(and corresponding electrodes 1 and/or 5) are a function of variouspreferred embodiments of the invention some of which are discussed ingreater detail in the “Examples” section herein. However, in general, aninput liquid 3 (for example water) is provided to a liquid transportmeans 40 (e.g., a liquid peristaltic pump or a liquid pumping means forpumping liquid 3) for pumping the liquid water 3 into the trough member30 at a first-end 31 thereof. For example, the input liquid 3 (e.g.,water) could be introduced calmly or could be introduced in an agitatedmanner. Agitation includes, typically, the introduction of nanobubblesor microbubbles, which may or may not be desirable. If a gentleintroduction is desired, then such input liquid 3 (e.g., water) could begently provided (e.g., flow into a bottom portion of the trough).Alternatively, a reservoir (not shown) could be provided above thetrough member 30 and liquid 3 could be pumped into such reservoir. Thereservoir could then be drained from a lower portion thereof, a middleportion thereof or an upper portion thereof as fluid levels providedthereto reached an appropriate level. The precise means for deliveringan input liquid 3 into the trough member 30 at a first end 31 thereof isa function of a variety of design choices. Further, as mentioned aboveherein, it should be understood that additional input portions 31 couldexist longitudinally along different portions of the trough member 30.The distance “c-c” is also shown in FIG. 14. In general, the distance“c-c” (which corresponds to center-to-center longitudinal measurementbetween each control device 20) can be any amount or distance whichpermits desired functioning of the embodiments disclosed herein. Thedistance “c-c” should not be less than the distance “y” (e.g., ¼″-2″; 6mm-51 mm) and in a preferred embodiment about 1.5″ (about 38 mm) shownin, for example, FIGS. 1-4 and 7-9. The Examples show various distances“c-c”, however, to give a general understanding of the distance “c-c”,approximate distances vary from about 4″ to about 8″ (about 102 mm toabout 203 mm) apart, however, more or less separation is of coursepossible (or required) as a function of application of all of theprevious embodiments disclosed herein. In the Examples disclosed laterherein, preferred distances “c-c” in many of the Examples are about7″-8″ (about 177-203 mm).

In general, the liquid transport means 40 may include any means formoving liquids 3 including, but not limited to a gravity-fed orhydrostatic means, a pumping means, a peristaltic pumping means, aregulating or valve means, etc. However, the liquid transport means 40should be capable of reliably and/or controllably introducing knownamounts of the liquid 3 into the trough member 30. Once the liquid 3 isprovided into the trough member 30, means for continually moving theliquid 3 within the trough member 30 may or may not be required.However, a simple means includes the trough member 30 being situated ona slight angle θ (e.g., less than one degree to a few degrees) relativeto the support surface upon which the trough member 30 is located. Forexample, the difference in vertical height between an inlet portion 31and an outlet portion 32 relative to the support surface may be all thatis required, so long as the viscosity of the liquid 3 is not too high(e.g., any viscosity around the viscosity of water can be controlled bygravity flow once such fluids are contained or located within the troughmember 30). In this regard, FIG. 15A shows cross-sectional views of thetrough member 30 forming an angle θ₁; and FIG. 15B shows across-sectional view of the trough member 30 forming an angle θ₂; and avariety of acceptable angles for trough member 30 that handle variousviscosities, including low viscosity fluids such as water. The anglesthat are desirable for different cross-sections of the trough member 30and low viscosity fluids typically range between a minimum of about0.1-5 degrees for low viscosity fluids and a maximum of 5-10 degrees forhigher viscosity fluids. However, such angles are a function of avariety of factors already mentioned, as well as, for example, whether aspecific fluid interruption means or a dam 80 is included along a bottomportion or interface where the liquid 3 contacts the trough member 30.Such flow interruption means could include, for example, partialmechanical dams or barriers along the longitudinal flow direction of thetrough member 30. In this regard, this approximately 5-10° and θ₂ isapproximately 0.1-5°. FIGS. 15A and 15B show a dam 80 near an outletportion 32 of the trough member 30. Multiple dam 80 devices can belocated at various portions along the longitudinal length of the troughmember 30. The dimension “j” can be, for example, about ⅛″-½″ (about3-13 mm) and the dimension “k” can be, for example, about V-¾″ (about6-19 mm). The cross-sectional shape (i.e., “j-k” shape) of the dam 80can include sharp corners, rounded corners, triangular shapes,cylindrical shapes, and the like, all of which can influence liquid 3flowing through various portions of the trough member 30.

Further, when viscosities of the liquid 3 increase such that gravityalone is insufficient, other phenomena such as specific uses ofhydrostatic head pressure or hydrostatic pressure can also be utilizedto achieve desirable fluid flow. Further, additional means for movingthe liquid 3 along the trough member 30 could also be provided insidethe trough member 30, Such means for moving the liquid 3 includemechanical means such as paddles, fans, propellers, augers, etc.,acoustic means such as transducers, thermal means such as heaters and orchillers (which may have additional processing benefits), etc. Theadditional means for moving the liquid 3 can cause liquid 3 to flow indiffering amounts in different portions along the longitudinal length ofthe trough member 30. In this regard, for example, if liquid 3 initiallyflowed slowly through a first longitudinal portion of the trough member30, the liquid 3 could be made to flow more quickly further downstreamthereof by, for example, as discussed earlier herein, changing thecross-sectional shape of the trough member 30. Additionally,cross-sectional shapes of the trough member 30 could also containtherein additional fluid handling means which could speed up or slowdown the rate the liquid 3 flows through the trough member 30.Accordingly, great flexibility can be achieved by the addition of suchmeans for moving the fluid 3.

FIG. 14 also shows a storage tank or storage vessel 41 at the end 32 ofthe trough member 30. Such storage vessel 41 can be any acceptablevessel and/or pumping means made of one or more materials which, forexample, do not negatively interact with the liquid 3 introduced intothe trough member 30 and/or products produced within the trough member30. Acceptable materials include, but are not limited to plastics suchas high density polyethylene (HDPE), glass, metal(s) (such a certaingrades of stainless steel), etc. Moreover, while a storage tank 41 isshown in this embodiment, the tank 41 should be understood as includinga means for distributing or directly bottling or packaging the liquid 3processed in the trough member 30.

FIGS. 16A, 16B and 16C show perspective views of one preferredembodiment of the invention. In these FIGS. 16A, 16B and 16C, eightseparate control devices 20 a-20 h are shown in more detail. Suchcontrol devices 20 can utilize one or more of the electrodeconfigurations shown in, for example, FIGS. 8A, 8B, 8C and 8D. Theprecise positioning and operation of the control devices 20 arediscussed in greater detail elsewhere herein. However, each of thecontrol devices 20 are separated by a distance “c-c” (see FIG. 14)which, in some of the preferred embodiments discussed herein, measuresabout 8″ (about 203 mm). FIG. 16B includes use of two air distributingor air handling devices (e.g., fans 342 a and 342 b); and FIG. 16Cincludes use of two alternative or desirable air handling devices 342 cand 342 d. The fans 342 a, 342 b, 342 c and/or 342 d can be any suitablefan. For example a Dynatron DF124020BA, DC brushless, 9000 RPM, ballbearing fan measuring about 40 mm×40 mm×20 mm works well. Specifically,this fan has an air flow of approximately 10 cubic feet per minute.

FIG. 17 shows another perspective view of another embodiment of theapparatus according to another preferred embodiment wherein six controldevices 20 a-20 f (i.e., six electrode sets) are rotated approximately90 degrees relative to the eight control devices 20 a-20 h shown inFIGS. 16A and 16B. Accordingly, the embodiment corresponds generally tothe electrode assembly embodiments shown in, for example, FIGS. 9A-9D.

FIG. 18 shows a perspective view of the apparatus shown in FIG. 16A, butsuch apparatus is now shown as being substantially completely enclosedby an atmosphere control apparatus 38. Such apparatus 38 is a means forcontrolling the atmosphere around the trough member 30, or can be usedto isolate external and undesirable material from entering into thetrough member 30 and negatively interacting therewith. Further, the exit32 of the trough member 30 is shown as communicating with a storagevessel 41 through an exit pipe 42. Moreover, an exit 43 on the storagetank 41 is also shown. Such exit pipe 43 can be directed toward anyother suitable means for storage, packing and/or handling the liquid 3.For example, the exit pipe 43 could communicate with any suitable meansfor bottling or packaging the liquid product 3 produced in the troughmember 30. Alternatively, the storage tank 41 could be removed and theexit pipe 42 could be connected directly to a suitable means forhandling, bottling or packaging the liquid product 3.

FIGS. 19A, 19B, 19C and 19D show additional cross-sectional perspectiveviews of additional electrode configuration embodiments which can beused according to the present invention.

In particular, FIG. 19A shows two sets of electrodes 5 (i.e., 4 totalelectrodes 5 a, 5 b, 5 c and 5 d) located approximately parallel to eachother along a longitudinal direction of the trough member 30 andsubstantially perpendicular to the flow direction “F” of the liquid 3through the trough member 30. In contrast, FIG. 19B shows two sets ofelectrodes 5 (i.e., 5 a, 5 b, 5 c and 5 d) located adjacent to eachother along the longitudinal direction of the trough member 30.

In contrast, FIG. 19C shows one set of electrodes 5 (i.e., 5 a, 5 b)located substantially perpendicular to the direction of fluid flow “F”and another set of electrodes 5 (i.e., 5 c, 5 d) located substantiallyparallel to the direction of the fluid flow “F”. FIG. 19D shows a mirrorimage of the electrode configuration shown in FIG. 19C. While each ofFIGS. 19A, 19B, 19C and 19D show only electrode(s) 5 it is clear thatelectrode(s) 1 could be substituted for some or all of thoseelectrode(s) 5 shown in each of FIGS. 19A-19D, and/or intermixed therein(e.g., similar to the electrode configurations disclosed in FIGS. 8A-8Dand 9A-9D). These alternative electrode configurations provide a varietyof alternative electrode configuration possibilities all of which canresult in different desirable nanoparticle or nanoparticle/solutions. Itshould now be clear to the reader that electrode assemblies locatedupstream of other electrode assemblies can provide raw materials, pHchanges, zeta potential changes, ingredients and/or conditioning orcrystal or structural changes to at least a portion of the liquid 3 suchthat reactions occurring at electrode(s) 1 and/or 5 downstream from afirst set of electrode(s) 1 and/or 5 can result in, for example, growthof nanoparticles, shrinking (e.g., partial or complete dissolution) ofnanoparticles, placing of different composition(s) on existingnanoparticles (e.g., surface feature comprising a variety of sizesand/or shapes and/or compositions which modify the performance of thenanoparticles), removing existing surface features or coatings onnanoparticles, changing and/or increasing or decreasing zeta potential,etc. In other words, by providing multiple electrode sets of multipleconfigurations and one or more atmosphere control devices along withmultiple adjustable electrochemical reactions and/or adjustable plasmas4, the variety of constituents produced, nanoparticles, compositenanoparticles, thicknesses of shell layers (e.g., partial or complete)coatings, zeta potential, or surface features on substratenanoparticles, are numerous, and the structure and/or composition of theliquid 3 can also be reliably controlled.

FIGS. 20A-20P show a variety of cross-sectional perspective views of thevarious electrode configuration embodiments possible and usable for allthose configurations of electrodes 1 and 5 corresponding only to theembodiment shown in FIG. 19A. In particular, for example, the number ofelectrodes 1 or 5 varies in these FIGS. 20A-20P, as well as the specificlocations of such electrode(s) 1 and 5 relative to each other. Ofcourse, these electrode combinations 1 and 5 shown in FIGS. 20A-20Pcould also be configured according to each of the alternative electrodeconfigurations shown in FIGS. 19B, 19C and 19D (i.e., sixteen additionalfigures corresponding to each of FIGS. 19B, 19C and 19D) but additionalfigures have not been included herein for the sake of brevity. Specificadvantages of these electrode assemblies, and others, are disclosed ingreater detail elsewhere herein.

As disclosed herein, each of the electrode configurations shown in FIGS.20A-20P, depending on the particular run conditions, can result indifferent products coming from the mechanisms, apparatuses and processesof the inventive disclosures herein.

FIGS. 21A, 21B, 21C and 21D show cross sectional perspective views ofadditional embodiments of the present invention. The electrodearrangements shown in these FIGS. 21A-21D are similar in arrangement tothose electrode arrangements shown in FIGS. 19A, 19B, 19C and 19D,respectively. However, in these FIGS. 21A-21D a membrane or barrierassembly 50 is also included. In these embodiments of the invention, amembrane 50 is provided as a means for separating different productsmade at different electrode sets so that any products made by the set ofelectrodes 1 and/or 5 on one side of the membrane 50 can be at leastpartially isolated, or segregated, or substantially completely isolatedfrom certain products made from electrodes 1 and/or 5 on the other sideof the membrane 50. This membrane means 50 for separating or isolatingdifferent products may act as a mechanical barrier, physical barrier,mechano-physical barrier, chemical barrier, electrical barrier, etc.Accordingly, certain products made from a first set of electrodes 1and/or 5 can be at least partially, or substantially completely,isolated from certain products made from a second set of electrodes 1and/or 5. Likewise, additional serially located electrode sets can alsobe similarly situated. In other words, different membrane(s) 50 can beutilized at or near each set of electrodes 1 and/or 5 and certainproducts produced therefrom can be controlled and selectively deliveredto additional electrode sets 1 and/or 5 longitudinally downstreamtherefrom. Such membranes 50 can result in a variety of differentcompositions of the liquid 3 and/or nanoparticles or ions present in theliquid 3 produced in the trough member 30.

Possible ion exchange membranes 50 which function as a means forseparating for use with the present invention include Anionic membranesand Cationic membranes. These membranes can be homogenous, heterogeneousor microporous, symmetric or asymmetric in structure, solid or liquid,can carry a positive or negative charge or be neutral or bipolar.Membrane thickness may vary from as small as 100 micron to several mm.

Some specific ionic membranes for use with certain embodiments of thepresent invention include, but are not limited to:

-   -   Homogeneous polymerization type membranes such as sulfonated and        aminated styrene-divinylbenzene copolymers    -   condensation and heterogeneous membranes    -   perfluorocarbon cation exchange membranes    -   membrane chlor-alkali technology    -   Most of cation and anion exchange membranes used in the        industrial area are composed of derivatives of        styrene-divinylbenzene copolymer,        chloromethylstyrene-divinylbenzene copolymer or        vinylpyridines-divinylbenzene copolymer.    -   The films used that are the basis of the membrane are generally        polyethylene, polypropylene (ref. ‘U, polytetrafluoroethylene,        PFA, FEP and so on.    -   Trifluoroacrylate and styrene are used in some cases.    -   Conventional polymers such as polyethersulfone, polyphenylene        oxide, polyvinyl chloride, polyvinylidene fluoride and so on.        Especially, sulfonation or chloromethylation and amination of        polyethersulfone or polyphenylene oxide.    -   Hydrocarbon ion exchange membranes are generally composed of        derivatives of styrene-divinylbenzene copolymer and other inert        polymers such as polyethylene, polyvinyl chloride and so on.

FIG. 22A shows a perspective cross-sectional view of an electrodeassembly which corresponds to the electrode assembly 5 a, 5 b shown inFIG. 9C. This electrode assembly can also utilize a membrane 50 forchemical, physical, chemo-physical and/or mechanical separation. In thisregard, FIG. 22B shows a membrane 50 located between the electrodes 5 a,5 b. It should be understood that the electrodes 5 a, 5 b could beinterchanged with the electrodes 1 in any of the multiple configurationsshown, for example, in FIGS. 9A-9C. In the case of FIG. 22B, themembrane assembly 50 has the capability of isolating partially orsubstantially completely, some or all of the products formed atelectrode 5 a, from some or all of those products formed at electrode 5b. Accordingly, various species formed at either of the electrodes 5 aand 5 b can be controlled so that they can sequentially react withadditional electrode assembly sets 5 a, 5 b and/or combinations ofelectrode sets 5 and electrode sets 1 in the longitudinal flow direction“F” that the liquid 3 undertakes along the longitudinal length of thetrough member 30. Accordingly, by appropriate selection of the membrane50, which products located at which electrode (or subsequent ordownstream electrode set) can be controlled. In a preferred embodimentwhere the polarity of the electrodes 5 a and 5 b are opposite, a varietyof different products may be formed at the electrode 5 a relative to theelectrode 5 b.

FIG. 22C shows another different embodiment of the invention in across-sectional schematic view of a completely different alternativeelectrode configuration for electrodes 5 a and 5 b. In this case,electrode(s) 5 a (or of course electrode(s) 1 a) are located above amembrane 50 and electrode(s) 5 b are located below a membrane 50 (e.g.,are substantially completely submerged in the liquid 3). In this regard,the electrode, 5 b can comprise a plurality of electrodes or may be asingle electrode running along at least some or the entire longitudinallength of the trough member 30. In this embodiment, certain speciescreated at electrodes above the membrane 50 can be different fromcertain species created below the membrane 50 and such species can reactdifferently along the longitudinal length of the trough member 30. Inthis regard, the membrane 50 need not run the entire length of thetrough member 30, but may be present for only a portion of such lengthand thereafter sequential assemblies of electrodes 1 and/or 5 can reactwith the products produced therefrom. It should be clear to the readerthat a variety of additional embodiments beyond those expresslymentioned here would fall within the spirit of the embodiments expresslydisclosed.

FIG. 22D shows another alternative embodiment of the invention whereby aconfiguration of electrodes 5 a (and of course electrodes 1) shown inFIG. 22C are located above a portion of a membrane 50 which extends atleast a portion along the length of a trough member 30 and a secondelectrode (or plurality of electrodes) 5 b (similar to electrode(s) 5 bin FIG. 22C) run for at least a portion of the longitudinal length alongthe bottom of the trough member 30. In this embodiment of utilizingmultiple electrodes 5 a, additional operational flexibility can beachieved. For example, by splitting the voltage and current into atleast two electrodes 5 a, the reactions at the multiple electrodes 5 acan be different from those reactions which occur at a single electrode5 a of similar size, shape and/or composition. Of course this multipleelectrode configuration can be utilized in many of the embodimentsdisclosed herein, but have not been expressly discussed for the sake ofbrevity. However, in general, multiple electrodes 1 and/or 5 (i.e.,instead of a single electrode 1 and/or 5) can add great flexibility inproducts produced according to the present invention. Details of certainof these advantages are discussed elsewhere herein.

FIG. 23A is a cross-sectional perspective view of another embodiment ofthe invention which shows a set of electrodes 5 corresponding generallyto that set of electrodes 5 shown in FIG. 19A, however, the differencebetween the embodiment of FIG. 23A is that a third set of electrode(s) 5e, 5 f have been provided in addition to those two sets of electrodes 5a, 5 b, 5 c and 5 d shown in FIG. 19A. Of course, the sets of electrodes5 a, 5 b, 5 c, 5 d, 5 d and 5 f can also be rotated 90 degrees so theywould correspond roughly to those two sets of electrodes shown in FIG.19B. Additional figures showing additional embodiments of those sets ofelectrode configurations have not been included here for the sake ofbrevity.

FIG. 23B shows another embodiment of the invention which also permutatesinto many additional embodiments, wherein membrane assemblies 50 a and50 b have been inserted between the three sets of electrodes 5 a, 5 b; 5c, 5 d; and 5 e, 5 f. It is of course apparent that the combination ofelectrode configuration(s), number of electrode(s) and precisemembrane(s) means 50 used to achieve separation includes manyembodiments, each of which can produce different products when subjectedto the teachings of the present invention. More detailed discussion ofsuch products and operations of the present invention are discussedelsewhere herein.

FIGS. 24A-24E; 25A-25E; and 26A-26E show cross-sectional views of avariety of membrane 50 locations that can be utilized according to thepresent invention. Each of these membrane 50 configurations can resultin different nanoparticles and/or nanoparticle/solution mixtures. Thedesirability of utilizing particular membranes in combination withvarious electrode assemblies add a variety of processing advantages tothe present invention. This additional flexibility results in a varietyof novel nanoparticle/nanoparticle solution mixtures.

Electrode Control Devices

The electrode control devices shown generally in, for example, FIGS. 2,3, 11, 12, 14, 16, 17 and 18 are shown in greater detail in FIG. 27 andFIGS. 28A-28L. In particular, FIG. 27 shows a perspective view of oneembodiment of an inventive control device 20. Further, FIGS. 28A-28Lshow perspective views of a variety of embodiments of control devices20. FIG. 28B shows the same control device 20 shown in FIG. 28A, exceptthat two electrode(s) 1 a/1 b are substituted for the two electrode(s) 5a/5 b.

First, specific reference is made to FIGS. 27, 28A and 28B. In each ofthese three FIGs., a base portion 25 is provided, said base portionhaving a top portion 25′ and a bottom portion 25″.

The base portion 25 is made of a suitable rigid plastic materialincluding, but not limited to, materials made from structural plastics,resins, polyurethane, polypropylene, nylon, teflon, polyvinyl, etc. Adividing wall 27 is provided between two electrode adjustmentassemblies. The dividing wall 27 can be made of similar or differentmaterial from that material comprising the base portion 25. Twoservo-step motors 21 a and 21 b are fixed to the surface 25′ of the baseportion 25. The step motors 21 a, 21 b could be any step motor capableof slightly moving (e.g., on a 360 degree basis, slightly less than orslightly more than 1 degree) such that a circumferential movement of thestep motors 21 a/21 b results in a vertical raising or lowering of anelectrode 1 or 5 communicating therewith. In this regard, a firstwheel-shaped component 23 a is the drivewheel connected to the outputshaft 231 a of the drive motor 21 a such that when the drive shaft 231 arotates, circumferential movement of the wheel 23 a is created. Further,a slave wheel 24 a is caused to press against and toward the drivewheel23 a such that frictional contact exists therebetween. The drivewheel 23a and/or slavewheel 24 a may include a notch or groove on an outerportion thereof to assist in accommodating the electrodes 1,5. Theslavewheel 24 a is caused to be pressed toward the drivewheel 23 a by aspring 285 located between the portions 241 a and 261 a attached to theslave wheel 24 a. In particular, a coiled spring 285 can be locatedaround the portion of the axis 262 a that extends out from the block 261a. Springs should be of sufficient tension so as to result in areasonable frictional force between the drivewheel 24 a and theslavewheel 24 a such that when the shaft 231 a rotates a determinedamount, the electrode assemblies 5 a, 5 b, 1 a, 1 b, etc., will move ina vertical direction relative to the base portion 25. Such rotational orcircumferential movement of the drivewheel 23 a results in a directtransfer of vertical directional changes in the electrodes 1,5 shownherein. At least a portion of the drivewheel 23 a should be made from anelectrically insulating material; whereas the slavewheel 24 a can bemade from an electrically conductive material or an electricallyinsulating material, but preferably, an electrically insulatingmaterial.

The drive motors 21 a/21 b can be any suitable drive motor which iscapable of small rotations (e.g., slightly below 1°/360° or slightlyabove 1°/360°) such that small rotational changes in the drive shaft 231a are translated into small vertical changes in the electrodeassemblies. A preferred drive motor includes a drive motor manufacturedby RMS Technologies model 1MC17-S04 step motor, which is a DC-poweredstep motor. This step motors 21 a/21 b include an RS-232 connection 22a/22 b, respectively, which permits the step motors to be driven by aremote control apparatus such as a computer or a controller.

With reference to FIGS. 27, 28A and 28B, the portions 271, 272 and 273are primarily height adjustments which adjust the height of the baseportion 25 relative to the trough member 30. The portions 271, 272 and273 can be made of same, similar or different materials from the baseportion 25. The portions 274 a/274 b and 275 a/275 b can also be made ofthe same, similar or different material from the base portion 25.However, these portions should be electrically insulating in that theyhouse various wire components associated with delivering voltage andcurrent to the electrode assemblies 1 a/1 b, 5 a/5 b, etc.

The electrode assembly specifically shown in FIG. 28A compriseselectrodes 5 a and 5 b (corresponding to, for example, the electrodeassembly shown in FIG. 3C). However, that electrode assembly couldcomprise electrode(s) 1 only, electrode(s) 1 and 5, electrode(s) 5 and1, or electrode(s) 5 only. In this regard, FIG. 28B shows an assemblywhere two electrodes 1 a/1 b are provided instead of the twoelectrode(s) 5 a/5 b shown in FIG. 28A. All other elements shown in FIG.28B are similar to those shown in FIG. 28A.

With regard to the size of the control device 20 shown in FIGS. 27, 28Aand 28B, the dimensions “L” and “W” can be any dimension whichaccommodates the size of the step motors 21 a/21 b, and the width of thetrough member 30. In this regard, the dimension “L” shown in FIG. 27needs to be sufficient such that the dimension “L” is at least as longas the trough member 30 is wide, and preferably slightly longer (e.g.,10-30%). The dimension “W” shown in FIG. 27 needs to be wide enough tohouse the step motors 21 a/21 b and not be so wide as to unnecessarilyunderutilize longitudinal space along the length of the trough member30. In one preferred embodiment of the invention, the dimension “L” isabout 7 inches (about 19 millimeters) and the dimension “W” is about 4inches (about 10.5 millimeters). The thickness “H” of the base member 25is any thickness sufficient which provides structural, electrical andmechanical rigidity for the base member 25 and should be of the order ofabout ¼″-¾″ (about 6 mm-19 mm). While these dimensions are not critical,the dimensions give an understanding of size generally of certaincomponents of one preferred embodiment of the invention.

Further, in each of the embodiments of the invention shown in FIGS. 27,28A and 28B, the base member 25 (and the components mounted thereto),can be covered by a suitable cover 290 (first shown in FIG. 28D) toinsulate electrically, as well as creating a local protectiveenvironment for all of the components attached to the base member 25.Such cover 290 can be made of any suitable material which providesappropriate safety and operational flexibility. Exemplary materialsinclude plastics similar to that used for other portions of the troughmember 30 and/or the control device 20 and is preferably transparent.

FIG. 28C shows a perspective view of an electrode guide assembly 280utilized to guide, for example, an electrode 5. Specifically, a topportion 281 is attached to the base member 25. A through-hole/slotcombination 282 a, 282 b and 282 c, all serve to guide an electrode 5therethrough. Specifically, the portion 283 specifically directs the tip9′ of the electrode 5 toward and into the liquid 3 flowing in the troughmember 30. The guide 280 shown in FIG. 28C can be made of materialssimilar, or exactly the same, as those materials used to make otherportions of the trough member 30 and/or base member 25, etc.

FIG. 28D shows a similar control device 20 as those shown in FIGS. 27and 28, but also now includes a cover member 290. This cover member 290can also be made of the same type of materials used to make the baseportion 25. The cover 290 is also shown as having 2 through-holes 291and 292 therein. Specifically, these through-holes can, for example, bealigned with excess portions of, for example, electrodes 5, which can beconnected to, for example, a spool of electrode wire (not shown in thesedrawings).

FIG. 28E shows the cover portion 290 attached to the base portion 25with the electrodes 5 a, 5 b extending through the cover portion 290through the holes 292, 291, respectively.

FIG. 28F shows a bottom-oriented perspective view of the control device20 having a cover 290 thereon. Specifically, the electrode guideapparatus 280 is shown as having the electrode 5 extending therethrough.More specifically, this FIG. 28F shows an arrangement where an electrode1 would first contact a fluid 3 flowing in the direction “F”, asrepresented by the arrow in FIG. 28F.

FIG. 28G shows the same apparatus as that shown in FIG. 28F with anatmosphere control device 35 added thereto. Specifically, the atmospherecontrol device is shown as providing a controlled atmosphere for theelectrode 1. Additionally, a gas inlet tube 286 is provided. This gasinlet tube provides for flow of a desirable gas into the atmospherecontrol device 35 such that plasmas 4 created by the electrode 1 arecreated in a controlled atmosphere.

FIG. 28H shows the assembly of FIG. 28G located within a trough member30 and a support means 341.

FIG. 28I is similar to FIG. 28F except now an electrode 5 is the firstelectrode that contacts a liquid 3 flowing in the direction of the arrow“F” within the trough member 30.

FIG. 28J corresponds to FIG. 28G except that the electrode 5 firstcontacts the flowing liquid 3 in the trough member 30.

FIG. 28K shows a more detailed perspective view of the underside of theapparatus shown in the other FIG. 28's herein.

FIG. 28L shows the control device 20 similar to that shown in FIGS. 28Fand 28I, except that two electrodes 1 are provided.

FIG. 29 shows another preferred embodiment of the invention wherein arefractory material 29 is combined with a heat sink 28 such that heatgenerated during processes practiced according to embodiments of theinvention generate sufficient amounts of heat that necessitate a thermalmanagement program. In this regard, the component 29 is made of, forexample, suitable refractory component, including, for example, aluminumoxide or the like. The refractory component 29 has a transversethrough-hole 291 therein which provides for electrical connections tothe electrode(s) 1 and/or 5. Further a longitudinal through-hole 292 ispresent along the length of the refractory component 29 such thatelectrode assemblies 1/5 can extend therethrough. The heat sink 28thermally communicates with the refractory member 29 such that any heatgenerated from the electrode assembly 1 and/or 5 is passed into therefractory member 29, into the heat sink 28 and out through the fins282, as well as the base portion 281 of the heat sink 28. The precisenumber, size, shape and location of the fins 282 and base portion 281are a function of, for example, the amount of heat required to bedissipated. Further, if significant amounts of heat are generated, acooling means such as a fan can be caused to blow across the fins 282.The heat sink is preferably made from a thermally conductive metal suchas copper, aluminum, etc.

FIG. 30 shows a perspective view of the heat sink of FIG. 29 as beingadded to the device shown in FIG. 27. In this regard, rather than theelectrode 5 a directly contacting the base portion 25, the refractorymember 29 is provided as a buffer between the electrodes 1/5 and thebase member 25.

A fan assembly, not shown in the drawings, can be attached to asurrounding housing which permits cooling air to blow across the coolingfins 282. The fan assembly could comprise a fan similar to a computercooling fan, or the like. A preferred fan assembly comprises, forexample, a Dynatron DF124020BA, DC brushless, 9000 RPM, ball bearing fanmeasuring about 40 mm×40 mm×20 mm works well. Specifically, this fan hasan air flow of approximately 10 cubic feet per minute.

FIG. 31 shows a perspective view of the bottom portion of the controldevice 20 shown in FIG. 30A. In this FIG. 31, one electrode(s) 1 a isshown as extending through a first refractory portion 29 a and oneelectrode(s) 5 a is shown as extending through a second refractoryportion 29 b. Accordingly, each of the electrode assemblies expresslydisclosed herein, as well as those referred to herein, can be utilizedin combination with the preferred embodiments of the control deviceshown in FIGS. 27-31. In order for the control devices 20 to beactuated, two general processes need to occur. A first process involveselectrically activating the electrode(s) 1 and/or 5 (e.g., applyingpower thereto from a preferred power source 10), and the second generalprocess occurrence involves determining how much power is applied to theelectrode(s) and appropriately adjusting electrode 1/5 height inresponse to such determinations (e.g., manually and/or automaticallyadjusting the height of the electrodes 1/5). In the case of utilizing acontrol device 20, suitable instructions are communicated to the stepmotor 21 through the RS-232 ports 22 a and 22 b. Important embodimentsof components of the control device 20, as well as the electrodeactivation process, are discussed later herein.

Power Sources

A variety of power sources are suitable for use with the presentinvention. Power sources such as AC sources of a variety of frequencies,DC sources of a variety of frequencies, rectified AC sources of variouspolarities, etc., can be used. However, in the preferred embodimentsdisclosed herein, an AC power source is utilized directly, or an ACpower source has been rectified to create a specific DC source ofvariable polarity.

FIG. 32A shows a source of AC power 62 connected to a transformer 60. Inaddition, a capacitor 61 is provided so that, for example, loss factorsin the circuit can be adjusted. The output of the transformer 60 isconnected to the electrode(s) 1/5 through the control device 20. Apreferred transformer for use with the present invention is one thatuses alternating current flowing in a primary coil 601 to establish analternating magnetic flux in a core 602 that easily conducts the flux.

When a secondary coil 603 is positioned near the primary coil 601 andcore 602, this flux will link the secondary coil 603 with the primarycoil 601. This linking of the secondary coil 603 induces a voltageacross the secondary terminals. The magnitude of the voltage at thesecondary terminals is related directly to the ratio of the secondarycoil turns to the primary coil turns. More turns on the secondary coil603 than the primary coil 601 results in a step up in voltage, whilefewer turns results in a step down in voltage.

Preferred transformer(s) 60 for use in various embodiments disclosedherein have deliberately poor output voltage regulation made possible bythe use of magnetic shunts in the transformer 60. These transformers 60are known as neon sign transformers. This configuration limits currentflow into the electrode(s) 1/5. With a large change in output loadvoltage, the transformer 60 maintains output load current within arelatively narrow range.

The transformer 60 is rated for its secondary open circuit voltage andsecondary short circuit current. Open circuit voltage (OCV) appears atthe output terminals of the transformer 60 only when no electricalconnection is present. Likewise, short circuit current is only drawnfrom the output terminals if a short is placed across those terminals(in which case the output voltage equals zero). However, when a load isconnected across these same terminals, the output voltage of thetransformer 60 should fall somewhere between zero and the rated OCV. Infact, if the transformer 60 is loaded properly, that voltage will beabout half the rated OCV.

The transformer 60 is known as a Balanced Mid-Point Referenced Design(e.g., also formerly known as balanced midpoint grounded). This is mostcommonly found in mid to higher voltage rated transformers and most 60mA transformers. This is the only type transformer acceptable in a“mid-point return wired” system. The “balanced” transformer 60 has oneprimary coil 601 with two secondary coils 603, one on each side of theprimary coil 601 (as shown generally in the schematic view in FIG. 33A).This transformer 60 can in many ways perform like two transformers. Justas the unbalanced midpoint referenced core and coil, one end of eachsecondary coil 603 is attached to the core 602 and subsequently to thetransformer enclosure and the other end of the each secondary coil 603is attached to an output lead or terminal. Thus, with no connectorpresent, an unloaded 15,000 volt transformer of this type, will measureabout 7,500 volts from each secondary terminal to the transformerenclosure but will measure about 15,000 volts between the two outputterminals.

In alternating current (AC) circuits possessing a line power factor or 1(or 100%), the voltage and current each start at zero, rise to a crest,fall to zero, go to a negative crest and back up to zero. This completesone cycle of a typical sinewave. This happens 60 times per second in atypical US application. Thus, such a voltage or current has acharacteristic “frequency” of 60 cycles per second (or 60 Hertz) power.Power factor relates to the position of the voltage waveform relative tothe current waveform. When both waveforms pass through zero together andtheir crests are together, they are in phase and the power factor is 1,or 100%. FIG. 33B shows two waveforms “V” (voltage) and “C” (current)that are in phase with each other and have a power factor of 1 or 100%;whereas FIG. 33C shows two waveforms “V” (voltage) and “C” (current)that are out of phase with each other and have a power factor of about60%; both waveforms do not pass through zero at the same time, etc. Thewaveforms are out of phase and their power factor is less than 100%.

The normal power factor of most such transformers 60 is largely due tothe effect of the magnetic shunts 604 and the secondary coil 603, whicheffectively add an inductor into the output of the transformer's 60circuit to limit current to the electrodes 1/5. The power factor can beincreased to a higher power factor by the use of capacitor(s) 61 placedacross the primary coil 601 of the transformer, 60 which brings theinput voltage and current waves more into phase.

The unloaded voltage of any transformer 60 to be used in the presentinvention is important, as well as the internal structure thereof.Desirable unloaded transformers for use in the present invention includethose that are around 9,000 volts, 10,000 volts, 12,000 volts and 15,000volts. However, these particular unloaded volt transformer measurementsshould not be viewed as limiting the scope acceptable power sources asadditional embodiments. A specific desirable transformer for use withvarious embodiments of the invention disclosed herein is made byFranceformer, Catalog No. 9060-P-E which operates at: primarily 120volts, 60 Hz; and secondary 9,000 volts, 60 mA.

FIGS. 32B and 32C show another embodiment of the invention, wherein theoutput of the transformer 60 that is input into the electrode assemblies1/5 has been rectified by a diode assembly 63 or 63′. The result, ingeneral, is that an AC wave becomes substantially similar to a DC wave.In other words, an almost flat line DC output results (actually a slight120 Hz pulse can sometimes be obtained). This particular assemblyresults in two additional preferred embodiments of the invention (e.g.,regarding electrode orientation). In this regard, a substantiallypositive terminal or output and substantially negative terminal oroutput is generated from the diode assembly 63. An opposite polarity isachieved by the diode assembly 63′. Such positive and negative outputscan be input into either of the electrode(s) 1 and/or 5. Accordingly, anelectrode 1 can be substantially negative or substantially positive;and/or an electrode 5 can be substantially negative and/or substantiallypositive. Further, when utilizing the assembly of FIG. 32B, it has beenfound that the assemblies shown in FIGS. 29, 30 and 31 are desirable. Inthis regard, the wiring diagram shown in FIG. 32B can generate more heat(thermal output) than that shown in, for example, FIG. 32A under a givenset of operating (e.g., power) conditions. Further, one or morerectified AC power source(s) can be particularly useful in combinationwith the membrane assemblies shown in, for example, FIGS. 21-26.

FIG. 34A shows 8 separate transformer assemblies 60 a-60 h each of whichis connected to a corresponding control device 20 a-20 h, respectively.This set of transformers 60 and control devices 20 is utilized in onepreferred embodiment discussed in the Examples section later herein.

FIG. 34B shows 8 separate transformers 60 a′-60 h′, each of whichcorresponds to the rectified transformer diagram shown in FIG. 32B. Thistransformer assembly also communicates with a set of control devices 20a-20 h and can be used as a preferred embodiment of the invention.

FIG. 34C shows 8 separate transformers 60 a″-60 h″, each of whichcorresponds to the rectified transformer diagram shown in FIG. 32C. Thistransformer assembly also communicates with a set of control devices 20a-20 h and can be used as a preferred embodiment of the invention.

Accordingly, each transformer assembly 60 a-60 h (and/or 60 a′-60 h′;and/or 60 a″-60 h″) can be the same transformer, or can be a combinationof different transformers (as well as different polarities). The choiceof transformer, power factor, capacitor(s) 61, polarity, electrodedesigns, electrode location, electrode composition, cross-sectionalshape(s) of the trough member 30, local or global electrode composition,atmosphere(s), local or global liquid 3 flow rate(s), liquid 3 localcomponents, volume of liquid 3 locally subjected to various fields inthe trough member 30, neighboring (e.g., both upstream and downstream)electrode sets, local field concentrations, the use and/or positionand/or composition of any membrane 50, etc., are all factors whichinfluence processing conditions as well as composition and/or volume ofconstituents produced in the liquid 3, nanoparticles andnanoparticle/solutions made according to the various embodimentsdisclosed herein. Accordingly, a plethora of embodiments can bepracticed according to the detailed disclosure presented herein.

Electrode Height Control/Automatic Control Device

A preferred embodiment of the invention utilizes the automatic controldevices 20 shown in various figures herein. The step motors 21 a and 21b shown in, for example, FIGS. 27-31, are controlled by an electricalcircuit diagrammed in each of FIGS. 35, 36A, 36B and 36C. In particular,the electrical circuit of FIG. 35 is a voltage monitoring circuit.Specifically, voltage output from each of the output legs of thesecondary coil 603 in the transformer 60 are monitored over the points“P-Q” and the points “P′-Q′”. Specifically, the resistor denoted by“R_(L)” corresponds to the internal resistance of the multi-metermeasuring device (not shown). The output voltages measured between thepoints “P-Q” and “P′-V′” typically, for several preferred embodimentsshown in the Examples later herein, range between about 200 volts andabout 4,500 volts. However, higher and lower voltages can work with manyof the embodiments disclosed herein. In the Examples later herein,desirable target voltages have been determined for each electrode set 1and/or 5 at each position along a trough member 30. Such desirabletarget voltages are achieved as actual applied voltages by, utilizing,for example, the circuit control shown in FIGS. 36A, 36B and 36C. TheseFIG. 36 refer to sets of relays controlled by a Velleman K8056 circuitassembly (having a micro-chip PIC16F630-I/P). In particular, a voltageis detected across either the “P-Q” or the “P′-Q′” locations and suchvoltage is compared to a predetermined reference voltage (actuallycompared to a target voltage range). If a measured voltage across, forexample, the points “P-Q” is approaching a high-end of a pre-determinedvoltage target range, then, for example, the Velleman K8056 circuitassembly causes a servo-motor 21 (with specific reference to FIG. 28A)to rotate in a clockwise direction so as to lower the electrode 5 atoward and/or into the fluid 3. In contrast, should a measured voltageacross either of the points “P-Q” or “P′-Q′” be approaching a lower endof a target voltage, then, for example, again with reference to FIG.28A, the server motor 21 a will cause the drive-wheel 23 a to rotate ina counter-clockwise position thereby raising the electrode 5 a relativeto the fluid 3.

Each set of electrodes in each embodiment of the invention has anestablished target voltage range. The size or magnitude of acceptablerange varies by an amount between about 1% and about 10%-15% of thetarget voltage. Some embodiments of the invention are more sensitive tovoltage changes and these embodiments should have, typically, smalleracceptable voltage ranges; whereas other embodiments of the inventionare less sensitive to voltage and should have, typically, largeracceptable ranges. Accordingly, by utilizing the circuit diagram shownin FIG. 35, actual voltages output from the secondary coil 603 of thetransformer 60 are measured at “R_(L)” (across the terminals “P-Q” and“P′-Q′”), and are then compared to the predetermined voltage ranges. Theservo-motor 21 responds by rotating a predetermined amount in either aclockwise direction or a counter-clockwise direction, as needed.Moreover, with specific reference to FIG. 36, it should be noted that aninterrogation procedure occurs sequentially by determining the voltageof each electrode, adjusting height (if needed) and then proceeding tothe next electrode. In other words, each transformer 60 is connectedelectrically in a manner shown in FIG. 35. Each transformer 60 andassociated measuring points “P-Q” and “P′-Q′” are connected to anindividual relay. For example, the points “P-Q” correspond to relaynumber 501 in FIG. 36A and the points “P′-Q′” correspond to the relay502 in FIG. 36A. Accordingly, two relays are required for eachtransformer 60. Each relay, 501, 502, etc., sequentially interrogates afirst output voltage from a first leg of a secondary coil 603 and then asecond output voltage from a second leg of the secondary coil 603; andsuch interrogation continues onto a first output voltage from a secondtransformer 60 b on a first leg of its secondary coil 603, and then onto a second leg of the secondary coil 603, and so on.

The computer or logic control for the disclosed interrogation voltageadjustment techniques are achieved by any conventional program orcontroller, including, for example, in a preferred embodiment, standardvisual basic programming steps utilized in a PC. Such programming stepsinclude interrogating, reading, comparing, and sending an appropriateactuation symbol to increase or decrease voltage (e.g., raise or loweran electrode relative to the surface 2 of the liquid 3). Such techniquesshould be understood by an artisan of ordinary skill.

Examples 1-12

The following examples serve to illustrate certain embodiments of theinvention but should not to be construed as limiting the scope of thedisclosure.

In general, each of the 12 Examples utilize certain embodiments of theinvention associated with the apparatuses generally shown in FIGS. 16Band 16C. Specific differences in processing and apparatus will beapparent in each Example. The trough member 30 was made from plexiglass,all of which had a thickness of about 3 mm-4 mm (about ⅛″). The supportstructure 34 was also made from plexiglass which was about ¼″ thick(about 6-7 mm thick). The cross-sectional shape of the trough member 30corresponded to that shape shown in FIG. 10B (i.e., a truncated “V”).The base portion “R” of the truncated “V” measured about 0.5″ (about 1cm), and each side portion “S”, “S′” measured about 1.5″ (about 3.75cm). The distance “M” separating the side portions “S”, “S′” of theV-shaped trough member 30 was about 2¼″-2 5/16″ (about 5.9 cm) (measuredfrom inside to inside). The thickness of each portion also measuredabout ⅛″ (about 3 mm) thick. The longitudinal length “L_(T)” (refer toFIG. 11A) of the V-shaped trough member 30 measured about 6 feet (about2 meters) long from point 31 to point 32. The difference in verticalheight from the end 31 of the trough member 30 to the end 32 was about¼-½″ (about 6-12.7 mm) over its 6 feet length (about 2 meters) (i.e.,less than 1°).

Purified water (discussed later herein) was used as the liquid 3 in allof Examples 1-12. The depth “d” (refer to FIG. 10B) of the water 3 inthe V-shaped trough member 30 was about 7/16″ to about ½″ (about 11 mmto about 13 mm) at various points along the trough member 30. The depth“d” was partially controlled through use of the dam 80 (shown in FIGS.15A and 15B). Specifically, the dam 80 was provided near the end 32 andassisted in creating the depth “d” (shown in FIG. 10B) to be about7/6″-½″ (about 11-13 mm) in depth. The height “j” of the dam 80 measuredabout ¼″ (about 6 mm) and the longitudinal length “k” measured about ½″(about 13 mm). The width (not shown) was completely across the bottomdimension “R” of the trough member 30. Accordingly, the total volume ofwater 3 in the V-shaped trough member 30 during operation thereof wasabout 26 in³ (about 430 ml).

The rate of flow of the water 3 in the trough member 30 was about150-200 ml/minute, depending on which Example was being practiced.Specifically, for example, silver-based and copper-basednanoparticle/solution raw materials made in Examples 1-3 and 5 allutilized a flow rate of about 200 ml/minute; and a zinc-basednanoparticle/solution raw material made in Example 4 utilized a flowrate of about 150 ml/minute. Such flow of water 3 was obtained byutilizing a Masterflex® L/S pump drive 40 rated at 0.1 horsepower,10-600 rpm. The model number of the Masterflex® pump 40 was 77300-40.The pump drive had a pump head also made by Masterflex® known asEasy-Load Model No. 7518-10. In general terms, the head for the pump 40is known as a peristaltic head. The pump 40 and head were controlled bya Masterflex® LS Digital Modular Drive. The model number for the DigitalModular Drive is 77300-80. The precise settings on the Digital ModularDrive were, for example, 150 milliliters per minute for Example 4 and200 ml/minute for the other Examples 1-3 and 5. Tygon® tubing having adiameter of ¼″ (i.e., size 06419-25) was placed into the peristaltichead. The tubing was made by Saint Gobain for Masterflex®. One end ofthe tubing was delivered to a first end 31 of the trough member 30 by aflow diffusion means located therein. The flow diffusion means tended tominimize disturbance and bubbles in water 3 introduced into the troughmember 30 as well as any pulsing condition generated by the peristalticpump 40. In this regard, a small reservoir served as the diffusion meansand was provided at a point vertically above the end 31 of the troughmember 30 such that when the reservoir overflowed, a relatively steadyflow of water 3 into the end 31 of the V-shaped trough member 30occurred.

Additionally, the plastic portions of the control devices 20 were alsomade from plexiglass having a thickness of about ⅛″ (about 3 mm). Withreference to FIG. 27, the control devices 20 had a dimension “w”measuring about 4″ (about 10 cm) and a dimension “L” measuring about7.5″ (about 19 cm). The thickness of the base portion 25 was about ¼″(about 0.5 cm). All of the other components shown in FIG. 27 are drawnvery close to scale. All individual components attached to surfaces 25′and 25″ were also made of plexiglass which were cut to size and gluedinto position.

With regard to FIGS. 16B and 16C, 8 separate electrode sets (Set 1, Set2, Set 3-Set 8) were attached to 8 separate control devices 20. Each ofTables 3-7 refers to each of the 8 electrode sets by “Set #”. Further,within any Set #, electrodes 1 and 5, similar to the electrodeassemblies shown in FIGS. 3A and 3C were utilized. Each electrode of the8 electrode sets was set to operate within specific target voltagerange. Actual target voltages are listed in each of Tables 3-7. Thedistance “c-c” (with reference to FIG. 14) from the centerline of eachelectrode set to the adjacent electrode set is also represented.Further, the distance “x” associated with any electrode(s) 1 utilized isalso reported. For any electrode 5's, no distance “x” is reported. Otherrelevant distances are reported, for example, in each of Tables 3-7.

The size and shape of each electrode 1 utilized was about the same. Theshape of each electrode 1 was that of a right triangle with measurementsof about 14 mm×23 mm×27 mm. The thickness of each electrode 1 was about1 mm. Each triangular-shaped electrode 1 also had a hole therethrough ata base portion thereof, which permitted the point formed by the 23 mmand 27 mm sides to point toward the surface 2 of the water 3. Thematerial comprising each electrode 1 was 99.95% pure (i.e., 3N5) unlessotherwise stated herein. When silver was used for each electrode 1, theweight of each electrode was about 2 grams. When zinc was used for eachelectrode 1, the weight of each electrode was about 1.1 grams. Whencopper was used for each electrode 1, the weight of each electrode wasabout 1.5 grams.

The wires used to attach the triangular-shaped electrode 1 to thetransformer 60 were, for Examples 1-4, 99.95% (3N5) silver wire, havinga diameter of about 1.016 mm. The wire used to attach the triangularshaped electrode 1 in Example 5 was 99.95% pure (3N5) copper wire, alsohaving a diameter of about 1.016 mm. Accordingly, a small loop of wirewas placed through the hole in each electrode 1 to electrically connectthereto.

The wires used for each electrode 5 comprised 99.95% pure (3N5) eachhaving a diameter of about 1.016 mm. The composition of the electrodes 5in Examples 1-3 was silver; in Example 4 was zinc and in Example 5 wascopper. All materials for the electrodes 1/5 were obtained from ESPIhaving an address of 1050 Benson Way, Ashland, Oreg. 97520.

The water 3 used in Examples 1-12 as an input into the trough member 30was produced by a Reverse Osmosis process and deionization process. Inessence, Reverse Osmosis (RO) is a pressure driven membrane separationprocess that separates species that are dissolved and/or suspendedsubstances from the ground water. It is called “reverse” osmosis becausepressure is applied to reverse the natural flow of osmosis (which seeksto balance the concentration of materials on both sides of themembrane). The applied pressure forces the water through the membraneleaving the contaminants on one side of the membrane and the purifiedwater on the other. The reverse osmosis membrane utilized several thinlayers or sheets of film that are bonded together and rolled in a spiralconfiguration around a plastic tube. (This is also known as a thin filmcomposite or TFC membrane.) In addition to the removal of dissolvedspecies, the RO membrane also separates out suspended materialsincluding microorganisms that may be present in the water. After ROprocessing a mixed bed deionization filter was used. The total dissolvedsolvents (“TDS”) after both treatments was about 0.2 ppm, as measured byan Accumet® AR20 pH/conductivity meter.

Example 1 Manufacturing Silver-Based Nanoparticles/NanoparticleSolutions AT059 and AT038

This Example utilizes 99.95% pure silver electrodes 1 and 5. Table 3summarizes portions of electrode design, location and operatingvoltages. As can be seen from Table 3, the target voltages were set to alow of about 550 volts and to a high of about 2,100 volts.

Further, bar charts of the actual and target voltages for each electrodein each of the 8 electrode sets, Set #1-Set #8, are shown in FIG. 37A.Still further, the actual recorded voltages as well as a function of thetime of day is shown in each of FIGS. 37B-37I. Accordingly, the datacontained in Table 3, as well as FIGS. 37A-37I, give a completeunderstanding of the electrode design in each electrode set as well asthe target and actual voltages applied to each electrode for theduration of the manufacturing process.

TABLE 3 AT059 Flow Rate: 200 ml/min Room Temperature 23 C. RelativeHumidity 23% Target Average Electrode Voltage Distance Distance VoltageSet # Set # (kV) “c-c” in/mm “x” in/mm (kV)  7/177.8* 1 1a 2.110.29/7.37 2.05 5a 1.83 N/A 1.83 8/203.2 2 1b 1.09 0.22/5.59 1.16 5b 1.14N/A 1.14 8/203.2 3 1c 1.02 0.22/5.59 0.96 5c 0.92 N/A 0.92 8/203.2 4 1d0.90 0.15/3.81 0.88 5d 0.78 N/A 0.77 9/228.6 5 1e 1.26 0.22/5.59 1.34 5e0.55 N/A 0.55 8/203.2 6 1f 0.96 0.22/5.59 0.99 5f 0.72 N/A 0.72 8/203.27 1g 0.89 0.22/5.59 0.81 5g 0.70 N/A 0.70 8/203.2 8 1h 0.63 0.15/3.810.59 5h 0.86 N/A 0.85  8/203.2** Output Water Temperature 67 C.*Distance from water inlet to center of first electrode set **Distancefrom center of last electrode set to water outlet

Example 2 Manufacturing Silver-Based Nanoparticles/NanoparticleSolutions AT060 and AT036

Table 4 contains information similar to that data shown in Table 3relating to electrode set design, voltages, distances, etc. It is clearfrom Table 4 that the electrode configurations Set #1 and Set #2 werethe same as of Set #'s 1-8 in Table 3 and Example 1. Further electrodeSets 3-8 are all configured in the same manner and corresponded to adifferent electrode configuration from Set #1 and Set #2 herein, whichelectrode configuration corresponds to that configuration shown in FIG.8C.

TABLE 4 AT060 Flow Rate: 200 ml/min Room Temperature 23 C. RelativeHumidity 23% Target Average Electrode Voltage Distance Distance VoltageSet # Set # (kV) “c-c” in/mm “x” in/mm (kV)  7/177.8* 1 1a 2.41 0.37/9.42.14 5a 1.87 N/A 1.86 8/203.2 2 1b 1.33 0.26/6.6 1.33 5b 1.13 N/A 1.138/203.2 3 5c 0.79 N/A 0.80  5c′ 0.78 N/A 0.79 8/203.2 4 5d 0.85 N/A 0.86 5d′ 0.88 N/A 0.91 9/228.6 5 5e 1.07 N/A 1.06  5e′ 0.70 N/A 0.69 8/203.26 5f 0.94 N/A 0.92  5f′ 0.92 N/A 0.90 8/203.2 7 5g 1.02 N/A 1.00  5g′0.93 N/A 0.91 8/203.2 8 5h 0.62 N/A 0.63  5h′ 0.80 N/A 0.83  8/203.2**Output Water Temperature 73 C. *Distance from water inlet to center offirst electrode set **Distance from center of last electrode set towater outlet

FIG. 38A shows a bar chart of target and actual average voltages foreach electrode in each of the 8 electrode sets (i.e., Set #1-Set #8).

FIGS. 38B-38I show actual voltages applied to the electrodes for each ofthe 8 electrode sets.

The product produced according to Example 2 is referred to herein as“AT060”.

Example 3 Manufacturing Silver-Based Nanoparticles/NanoparticleSolutions AT031

Table 5 herein sets forth electrode design and target voltages for eachof the 16 electrodes in each of the eight electrode sets (i.e., Set#1-Set #8) utilized to form the product formed in this example referredto herein as “AT031”.

TABLE 5 AT031 Flow Rate: 200 ml/min Room Temperature 22.5 C. RelativeHumidity 47% Target Average Electrode Voltage Distance Distance VoltageSet # Set # (kV) “c-c” in/mm “x” in/mm (kV)  7/177.8* 1 1a 2.240.22/5.59 2.28 5a 1.84 N/A 1.84 8/203.2 2 5b 1.35 N/A 1.36  5b′ 1.55 N/A1.55 8/203.2 3 5c 1.46 N/A 1.46  5c′ 1.54 N/A 1.54 8/203.2 4 1d 1.620.19/4.83 1.61 5d 1.25 N/A 1.27 9/228.6 5 5e 1.21 N/A 1.21  5e′ 0.82 N/A0.82 8/203.2 6 5f 0.99 N/A 1.06  5f′ 0.92 N/A 0.92 8/203.2 7 5g 1.02 N/A1.03  5g′ 0.96 N/A 0.95 8/203.2 8 5h 1.00 N/A 1.00  5h′ 0.97 N/A 1.23 8/203.2** Output Water Temperature 83 C. *Distance from water inlet tocenter of first electrode set **Distance from center of last electrodeset to water outlet

FIG. 39A shows a bar chart of target and actual average voltages appliedfor each of the 16 electrodes in each of the 8 electrode sets.

FIGS. 39B-39I show the actual voltages applied to each of the 16electrodes in each of the 8 electrode sets as a function of time.

It should be noted that electrode Set #1 was the same in this Example 3as in each of Examples 1 and 2 (i.e., an electrode configuration of1/5). Another 1/5 configuration was utilized for each of the otherelectrode sets, namely Set #2 and Set #'s 5-8 were all configured in amanner according to a 5/5 configuration.

Example 4 Manufacturing Zinc-Based Nanoparticles/Nanoparticle SolutionsBT006 and BT004

Material designated herein as “BT006” was manufactured in accordancewith the disclosure of Example 4. Similar to Examples 1-3, Table 6herein discloses the precise electrode combinations in each of the 8electrode sets (i.e, Set #1-Set #8). Likewise, target and actualvoltage, distances, etc., are also reported. It should be noted that theelectrode set assembly of Example 4 is similar to the electrode setassembly used in Example 1, except that 99.95% pure zinc was used onlyfor the electrodes 5. The triangular-shaped portion of the electrodes 1also comprised the same purity zinc, however the electrical connectionsto the triangular-shaped electrodes were all 99.95% pure silver-wire,discussed above herein. Also, the flow rate of the reaction 3 was lowerin this Example then in all the other Examples.

TABLE 6 BT006 Flow Rate: 150 ml/min Room Temp 73.2-74.5 F. Relativehumidity 21-22% Target Average Electrode Voltage Distance DistanceVoltage Set # Set # (kV) ″c-c″ in/mm ″x″ in/mm (kV) 7/177.8*  1 1a 1.910.29/7.37 1.88 5a 1.64 N/A 1.64 8/203.2  2 1b 1.02 0.22/5.59 1.05 5b1.09 N/A 1.08 8/203.2  3 1c 0.91 0.22/5.59 0.90 5c 0.81 N/A 0.828/203.2  4 1d 0.84 0.15/3.81 0.86 5d 0.74 N/A 0.75 9/228.6  5 1e 1.400.22/5.59 1.40 5e 0.54 N/A 0.55 8/203.2  6 1f 0.93 0.22/5.59 0.91 5f0.61 N/A 0.63 8/203.2  7 1g 0.72 0.22/5.59 0.82 5g 0.75 N/A 0.758/203.2  8 1h 0.64 0.15/3.81 0.60 5h 0.81 N/A 0.81 8/203.2** OutputWater Temperature 64 C. *Distance from water inlet to center of firstelectrode set **Distance from center of last electrode set to wateroutlet

FIG. 40A shows a bar chart of the target and actual applied averagevoltages utilized for each of the 16 electrodes in the 8 electrode sets.Also, FIGS. 40B-40I show the actual voltages applied to each of the 16electrodes as a function of time.

Example 5 Manufacturing Copper-Based Nanoparticles/NanoparticleSolutions CT006

A copper-based nanoparticle solution designated as “CT006” was madeaccording to the procedures disclosed in Example 5. In this regard,Table 7 sets forth pertinent operating parameters associated with eachof the 16 electrodes in the 8 electrode sets.

TABLE 7 CT006 Flow Rate: 200 ml/min Relative Humidity 48% RoomTemperature 23.1 C. Target Average Electrode Voltage Distance DistanceVoltage Set # Set # (kV) ″c-c″ (in) ″x″ (in) (kV) 7/177.8*  1 1a 2.170.44/11.18 2.21 5a 1.75 N/A 1.74 8/203.2  2 5b 1.25 N/A 1.24  5b′ 1.64N/A 1.63 8/203.2  3 1c 1.45 0.22/5.59  1.43 5c 0.83 N/A 0.83 8/203.2  45d 0.77 N/A 0.77  5d′ 0.86 N/A 0.86 9/228.6  5 5e 1.17 N/A 1.15  5e′0.76 N/A 0.76 8/203.2  6 5f 0.85 N/A 0.84  5f′ 0.84 N/A 0.83 8/203.2  75g 0.99 N/A 0.99  5g′ 0.87 N/A 0.86 8/203.2  8 5h 0.85 N/A 0.85  5h′1.10 N/A 1.09 8/203.2** Output Water Temperature 79 C. *Distance fromwater inlet to center of first electrode set **Distance from center oflast electrode set to water outlet

Further, FIG. 41A shows a bar chart of each of the average actualvoltages applied to each of the 16 electrodes in the 8 electrode sets.It should be noted that the electrode configuration was slightlydifferent than the electrode configuration in each of Examples 1-4.Specifically, electrode Set #'s 1 and 3 were of the 1/5 configuration,and all other the Sets were of the 5/5 configuration.

FIG. 41B-41I show the actual voltages applied to each of the 16electrodes as a function of time. As above, the wires utilized for eachof the electrode(s) 1 and 5 comprised wires of a diameter of about 0.04″(1.016 mm) and a 99.95% purity.

Characterization of Materials of Examples 1-5 and Mixtures Thereof

Each of the silver-based nanoparticles and nanoparticle/solutions madein Examples 1-3 (AT-059/AT-038), (AT060/AT036) and (AT031),respectively; as well as the zinc nanoparticles andnanoparticle/solutions made in Example 4 (BT-004); and the coppernanoparticles and nanoparticle-based/solutions made in Example 5(CT-006) were physically characterized by a variety of techniques.Specifically, Tables 8 and 9 herein show each of the 5 “raw materials”made according to Examples 1-5 as well as 10 solutions or mixtures madetherefrom, each of the solutions being designated “GR1-GR10” orGR1B-GR10B”. The amount by volume of each of the “raw materials” isreported for each of the 10 solutions manufactured. Further, atomicabsorption spectroscopy (“AAS”) was performed on each of the rawmaterials of Examples 1-5 as well as on each of the 10 solutionsGR1-GR10 derived therefrom. The amount of silver constituents, zincconstituents and/or copper constituents therein were thus determined.The atomic absorption spectroscopy results (AAS) are reported bymetallic-based constituent.

TABLE 8 Solution Contents Analytical Results Silver % by Zinc % byCopper % by Ag ppm Zn ppm Cu ppm Metal ppm NO2 NO3 ID Constituent VolumeConstituent Volume Constituent Volume (AAS) (AAS) (AAS) (Ionic) (ppm)(ppm) pH AT-036 AT-036 100.0% 43.8 30.8 38.9 2.3 5.31 AT-031 AT-031100.0% 41.3 23.3 41.3 15 5.23 AT-038 AT-038 100.0% 46 24.3 N/A 11.7 3.34BT-004 BT-004 100.0% 23.1 ** N/A 33.7 3.52 CT-006 CT-006 100.0% 9.2 17.35.20 4.38 GR1  AT-036  22.8% BT-004  43.3% CT-006  33.9% 9.4 10.5 3.3 *6.2 19.7 3.93 GR2  AT-031  24.2% BT-004  43.3% CT-006  32.5% 8.7 11.42.9 * 7.2 21.5 3.86 GR3  AT-038  21.7% BT-004  43.3% CT-006  35.0% 9.110.8 3.1 * N/A 23.7 3.64 GR4  AT-036  22.8% BT-004  77.2% 9.5 19.7 5.6N/A 36.7 3.66 GR5  AT-031  24.2% BT-004  75.8% 10.4 18.8 5.9 N/A 26.63.68 GR6  AT-038  21.7% BT-004  78.3% 7.6 N/A 25.3 3.5  GR7  AT-036 45.7% BT-004  54.3% 17.3 13.3 8.9 N/A 19.6 3.83 GR8  AT-036  16.0%BT-004  84.0% 7.4 20.0 5.1 N/A 29.2 3.61 GR9  AT-036  70.0% BT-004 10.0% CT-006  20.0% 27.1 2.4 1.8 * 36.2 3.1 4.54 GR10 AT-36/31/39 34.3% BT-004  65.7% 13.2 15.6 7.3 N/A 23.4 3.62 N/A = pH is out oftesting range * Can not be tested due to silver and copper interaction** Zinc can not be tested with device

The AAS values were obtained from a Perkin Elmer AAnalyst 300Spectrometer system. The samples from Examples 1-5 and SolutionsGR1-GR10 were prepared by adding a small amount of nitric acid orhydrochloric acid (usually 2% of final volume) and then dilution to adesirable characteristic concentration range or linear range of thespecific element to improve accuracy of the result. The “desireable”range is an order of magnitude estimate based on production parametersestablished during product development. For pure metals analysis, aknown amount of feedstock material is digested in a known amount of acidand diluted to ensure that the signal strength of the absorbance will bewithin the tolerance limits and more specifically the most accuraterange of the detector settings, better known as the linear range.

The specific operating procedure for the Perkin Elmer AAnalyst 300system is as follows:

I) Principle

-   -   The Perkin Elmer AAnalyst 300 system consists of a high        efficiency burner system with a Universal GemTip nebulizer and        an atomic absorption spectrometer. The burner system provides        the thermal energy necessary to dissociate the chemical        compounds, providing free analyte atoms so that atomic        absorption occurs. The spectrometer measures the amount of light        absorbed at a specific wavelength using a hollow cathode lamp as        the primary light source, a monochromator and a detector. A        deuterium arc lamp corrects for background absorbance caused by        non-atomic species in the atom cloud.

II) Instrument Setup

-   -   A) Empty waste container to mark. Add deionized water to drain        tubing to ensure that water is present in the drain system float        assembly.    -   B) Ensure that the appropriate Hollow Cathode Lamp for the        analyte to be analyzed is properly installed in the turret.    -   C) Power AAnalyst 300 and computer ON.    -   E) After the AAnalyst 300 has warmed up for approximately 3        minutes, start the AAWin Analyst software    -   F) Recall Method to be analyzed.    -   G) Ensure that the correct Default Conditions are entered.    -   H) Align the Hollow Cathode Lamp.        -   1) Check that a proper peak and energy level has been            established for the specific lamp.        -   2) Adjust the power and frequency of the lamp settings to            obtain maximum energy.    -   I) Store Method changes in Parameter Entry, Option, Store and #.    -   J) Adjust Burner height.        -   1) Place a white sheet of paper behind the burner to confirm            the location of the light beam.        -   2) Lower the burner head below the light beam with the            vertical adjustment knob.        -   3) Press Cont (Continuous) to display an absorbance value.        -   4) Press A/Z to Autozero.        -   5) Raise the burner head with the vertical adjustment knob            until the display indicates a slight absorbance (0.002).            Slowly lower the head until the display returns to zero.            Lower the head an additional quarter turn to complete the            adjustment.    -   K) Ignite flame.        -   1) Turn Fume Hood switch ON.        -   2) Open air compressor valve. Set pressure to 50 to 65 psi.        -   3) Open acetylene gas cylinder valve. Set output pressure to            12 to 14 psi. Replace cylinder when pressure falls to 85 psi            to prevent valve and tubing damage from the presence of            acetone.        -   4) Press Gases On/Off. Adjust oxidant flow to 4 Units.        -   5) Press Gases On/Off. Adjust acetylene gas flow to 2 Units.        -   6) Press Flame On/Off to turn flame on.            -   Note: Do not directly view the lamp or flame without                protective ultraviolet radiation eyewear.    -   L) Aspirate deionized water through the burner head several        minutes.    -   M) Adjust Burner Position and Nebulizer.        -   1) Aspirate a standard with a signal of approximately 0.2            absorbance units.        -   2) Obtain maximum burner position absorbance by rotating the            horizontal and rotational adjustment knobs.        -   3) Loosen the nebulizer locking ring by turning it            clockwise. Slowly turn the nebulizer adjustment knob to            obtain maximum absorbance. Lock the knob in place with the            locking ring.        -   Note: An element, such as Magnesium, which is at a            wavelength where gases do not absorb is optimal for            adjusting the Burner and Nebulizer.    -   N) Allow 30 minutes to warm-up flame and lamp.

III) Calibration Procedure

-   -   A) Calibrate with standards that bracket the sample        concentrations.    -   B) WinAA Analyst software will automatically create a        calibration curve for your sample readings. But check to ensure        that proper absorption is established with each calibration        standard.    -   C) Enter Standard Concentration Values in the Default Conditions        to calculate an AAnalyst 300 standard curve.        -   1) Enter the concentration of the lowest standard for STD1            using significant digits.        -   2) Enter the concentrations of the other standards of the            calibration curve in ascending order and the concentration            of the reslope standard.        -   3) Autozero with the blank before each standard.        -   4) Aspirate Standard 1, press 0 Calibrate to clear the            previous curve. Aspirate the standards in numerical order.        -   Press standard number and calibrate for each standard.        -   5) Press Print to print the graph and correlation            coefficient.        -   6) Rerun one or all standards, if necessary. To rerun            Standard 3, aspirate standard and press 3 Calibrate.        -   7) Reslope the standard curve by pressing Reslope after            aspirating the designated reslope standard.    -   D) The correlation coefficient should be greater than or equal        to 0.990.    -   E) Check the calibration curve for drift, accuracy and precision        with standards and controls every 20 samples.

IV) Analysis Procedure

-   -   A) Autozero with the blank before each standard, control and        sample.    -   B) Aspirate sample and press Read Sample. The software will take        3 readings of absorbance and then average those readings. Wait        until software says idle. Rerun the sample if the standard        deviation is greater than 10% of the sample result.

V) Instrument Shutdown

-   -   A) Aspirate 5% Hydrochloric Acid (HCl) for 5 minutes and        deionized water for 10 minutes to clean the burner head. Remove        the capillary tube from the water.    -   B) Press Flame On/Off to turn off flame.    -   C) Close air compressor valve.    -   D) Close acetylene cylinder valve.    -   E) Press Bleed Gases to bleed the acetylene gas from the lines.        The cylinder pressure should drop to zero.    -   F) Exit the software, power OFF the AAnalyst 300, and shut down        the computer.

Further, the last 4 columns of Table 8 disclose “Metal PPM (Ionic)”; andO₂ (ppm); NO₃ (ppm); and “pH”. Each of these sets of numbers weredetermined by utilizing an ion selective electrode measurementtechnique. In particular, a NICO ion analyzer was utilized. Precisestabilization times and actual experimental procedures for collectingthe data in each of these three columns of Table 8 (and Table 9) occursimmediately below.

DEFINITIONS

Stabilization Times—After immersing the electrodes in a new solution,the mV reading normally falls rapidly at first by several mV, and thengradually, and increasingly slowly, falls to a stable reading as the ISEmembrane equilibrates and the reference electrode liquid junctionpotential stabilizes. This equilibration may take up to 3 or 4 minutesto reach a completely stable value. Sometimes the reading begins to riseagain after a short period of stability and it is important to ensurethat the recording is made at the lowest point, before this rise hasproceeded to any great extent. In this study it was found that it wasnot necessary to wait for a completely stable reading but thatsatisfactory results could be obtained by taking a reading after apre-set time, so that each measurement was made at the same point of thedecay curve. For optimum performance it was found that this delay timeshould be at least two minutes to ensure that the reading was in theshallower part of the curve.

Procedure:

-   -   1. Obtain two 150 mL beakers for each electrode to be used        (typically 4). One beaker will be used for the solutions        themselves and the other beaker will be filled with DI H2O to        equalize the membranes of each electrode after each solution has        been tested.    -   2. Obtain approximately 50 mL of the solution of interest for        each electrode being used and its respective beaker. (Commonly        about 200 mL for testing of Ag, NO3, NO2 and pH of a solution.)    -   3. If not already in place, locate and insert each desired ion        selective electrode and its respective reference electrode into        the appropriate receptacle. Only one electrode and its reference        electrode per receptacle unless both ion selective electrodes        require the use of the same reference electrode. Remove caps        from each electrode and its corresponding reference electrode        and place them into the electrode holder.    -   4. Turn on the computer associated with the NICO Ion Analyser        and the software to operate it.    -   5. Open the 8-Channel Ion Electrode Analyser Software to operate        the equipment.    -   6. Each ion selective electrode must be calibrated using the        standards most accurate for our purposes. This calibration must        be done each time the machine is turned on and for most accurate        results, should be calibrated before each individual sample is        tested. For each ion selective electrode, at the present time, 1        ppm, 10 ppm and 100 ppm give the best calibration for our        solutions and their relative readings. Locate the “Calibrate”        button on the software interface and follow the directions.    -   7. Each beaker is to be rinsed with DI H2O and swabbed with a        lint free cloth before each use.    -   8. Fill each “solution” beaker with approximately 50 mL of the        solution of interest and each “equalizer” beaker with        approximately 100 mL of DI H2O.    -   9. Place each electrode into the “equalizer” beakers for        approximately 15 seconds to ensure the membranes are in the same        state and equal before each new solution is tested.    -   10. Remove electrodes from the DI H2O and wipe gently with a        lint free cloth.    -   11. Place the electrodes into the solution so that each        electrode and reference electrode is immersed at least 2 cm.        Gently swirl the electrode and beaker to ensure homogeneity and        good to remove any air bubbles that may be between the        electrodes and the solution.    -   12. Let the electrodes remain undisturbed for 2-5 minutes        depending on the stabilization time for the particular solution.    -   13. When the operator is satisfied with the reading and it        occurs during the stabilization time, it must be recorded using        the software. Upon hitting the “Record” button you will be        prompted for a filename for this specific set of data. Also        record these readings in a lab book that can be used for        transferring numbers to external speadsheets and the like.    -   14. Remove the electrodes from the solution and discard the        solution.    -   15. Rinse each electrode with a stream of DI H2O.    -   16. Rinse each 150 mL beaker with DI H2O.    -   17. Dry both the electrodes and the beakers with lint free        cloths.    -   18. Return each electrode to its holder and replace caps if no        further testing is to occur.

Table 9 is also included herein which contains similar data to that datashown in Table 8 (and discussed in Examples 1-5) with the only exceptionbeing AT-031. The data in Table 9 comes from procedures copied fromExamples 1-5 except that such procedures were conducted at a much laterpoint in time (months apart). The raw materials and associatedsolutions, summarized in Table 9 show that the raw materials, as well assolutions therefrom, are substantially constant. Accordingly, theprocess is very reliable and reproducible.

TABLE 9 Solution Contents Analytical Results Silver % by Zinc % byCopper % by Ag ppm Zn ppm Cu ppm Metal ppm NO2 NO3 ID Constituent VolumeConstituent Volume Constituent Volume (AAS) (AAS) (AAS) (Ionic) (ppm)(ppm) pH AT-060 AT-060 100.0% 40.9 24.2 N/A 0.00 4.04 AT-031 AT-031100.0% 41.3 23.3 41.3 15 5.23 AT-059 AT-059 100.0% 41.4 10.9 N/A 13.32.98 BT-006 BT-006 100.0% 24 ** N/A 20.8 3.13 CT-006 CT-006 100.0% 9.2 17.3 5.20 4.38 GR1B  GR2B  GR3B  AT-059  24.2% BT-006  41.7% CT-006 34.2% 9.99 9.85 2.91 * N/A 58 3.27 GR4B  GR5B  AT-031  24.2% BT-006 75.8% 9.34 18.8 5.5 N/A 42.8 3.25 GR6B  GR7B  AT-060  48.9% BT-006 51.1% 20.6 12.7 8.7 N/A 30.5 3.38 GR8B  AT-060  17.1% BT-006  82.9%7.13 19.1 5 N/A 39.4 3.2  GR9B  AT-060  70.0% BT-006  10.0% CT-006 20.0% 29.9 3.7 1.7 * N/A 15.8 3.82 GR10B AT-60/31/59  36.4% BT-006 63.6% 14.2 15.6 7 N/A 21.4 3.2  N/A = pH is out of testing range * Cannot be tested due to silver and copper interaction ** Zinc can not betested with device

Scanning Electron Microscopy/Eds

Scanning electron microscopy was performed on each of the new materialsand solutions GR1-GR10 made according to Examples 1-5.

FIGS. 42A-42E show EDS results for a scanning electron microscopecorresponding to each of the 5 raw materials made in Examples 1-5,respectively.

FIGS. 42F-42O show EDS analysis for each of the 10 solutions shown inTables 8 and 9.

XEDS spectra were obtained using a EDAX Lithium drifted silicon detectorsystem coupled to a IXRF Systems digital processor, which was interfacedwith an AMRAY 1820 SEM with a LaB6 electron gun. Interpretation of allspectra generated was performed using IXRF EDS2008, version 1.0 Rev Edata collection and processing software.

Instrumentation hardware and software setup entails positioning liquidsamples from each Run ID on a sample stage in such a manner within theSEM to permit the area of interest to be under the electron beam forimaging purposes while allowing emitted energies to have optimum path tothe XEDS detector. A sample is typically positioned about 18 mm beneaththe aperture for the final lens and tilted nominally at 18° towards theXEDS detector. All work is accomplished within a vacuum chamber,maintained at about 10⁻⁶ torr.

The final lens aperture is adjusted to 200 to 300 μm in diameter and thebeam spot size is adjusted to achieve an adequate x-ray photon countrate for the digital “pulse” processor. Data collection periods rangebetween 200 and 300 seconds, with “dead-times” of less than 15%.

An aliquot of liquid sample solution is placed onto a AuPd sputteredglass slide followed by a dehydration step which includes freeze dryingthe solution or drying the solution under a dry nitrogen gas flow toyield particulates from the suspension. Due to the nature of theparticulates, no secondary coating is required for either imaging orXEDS analysis.

FIGS. 43A(A-D)-43E(A-D) disclose photomicrographs, at 4 differentmagnifications each, corresponding to freeze-drying each of thematerials produced in Examples 1-5, as well as freeze drying each of thesolutions GR1-GR10 recorded in Tables 8 and 9. Specifically, FIGS.43F(A-D)-430(A-D) correspond to the solutions GR1-GR10, respectively.All of the photomicrographs were generated with an AMRAY 1820 SEM withan LaB6 electron gun. Magnification size lens are shown on eachphotomicrograph.

Transmission Electron Microscopy

Transmission Electron Microscopy was performed on raw materialscorresponding to the components used to manufacture GR5 and GR8, as wellas the solutions GR5 and GR8. Specifically, an additional run wasperformed corresponding to those production parameters associated withmanufacturing AT031 (i.e, the silver constituent in GR5); an additionalrun was performed corresponding to those production parametersassociated with manufacturing AT060 (i.e., the silver constituent inGR8); and an additional run was performed corresponding to thoseproduction parameters associated with manufacturing BT006 (i.e., thezinc constituent used in both GR5 and GR8). The components were thenmixed together in a similar manner as discussed above herein to resultin solutions equivalent to previously manufactured GR5 and GR8.

FIGS. 43P(A)-43P(C) disclose three different magnification TEMphotomicrographs of a silver constituent made corresponding to theproduction parameters used to manufacture AT031.

FIGS. 43Q(A)-43Q(F) disclose six different TEM photomicrographs taken atthree different magnifications of a silver constituent madecorresponding to the production parameters used to manufacture AT060.

FIGS. 43R(A)-43R(B) disclose two different TEM photomicrographs taken attwo different magnifications of a zinc constituent made according to theproduction parameters used to manufacture BT006.

FIGS. 43S(A)-43S(E) disclose five different TEM photomicrographs takenat three different magnifications of a solution GR5.

FIGS. 43T(A)-43T(J) disclose ten different TEM photomicrographs taken atthree different magnifications of a solution GR8.

The samples for each of the TEM photomicrographs were prepared at roomtemperature. Specifically, 4 microliters of each liquid sample wereplaced onto a holey carbon film which was located on top of filter paper(used to wick off excess liquid). The filter paper was moved to a dryspot and this procedure was repeated resulting in 8 total microliters ofeach liquid sample being contacted with one portion of the holey carbonfilm. The carbon film grids were then mounted in a single tilt holderand placed in the loadlock of the JEOL 2100 CryoTEM to pump for about 15minutes. The sample was then introduced into the column and the TEMmicroscopy work performed.

The JEOL 2100 CryoTEM operated at 200 kv accelerating potential. Imageswere recorded on a Gatan digital camera of ultra high sensitivity.Typical conditions were 50 micron condenser aperture, spot size 2, andalpha 3.

These TEM photomicrographs show clearly that the average particle sizeof those particles in FIG. 43P (i.e., those corresponding to the silverconstant in GR05) are smaller than those particles shown in FIG. 43Q(i.e., those corresponding to the silver constituent in GR8). Further,crystal planes are clearly shown in both sets of FIGS. 43P and 43Q.Moreover, FIG. 43Q show the development of distinct crystal facets, someof which correspond to the known 111 cubic structure for silver.

TEM photomicrographs 43 r do not show any significant crystallization ofzinc.

TEM photomicrographs 43 s (corresponding to solution GR5) also showsimilar silver features as shown in FIG. 43P; and the photomicrographs43 t (i.e., corresponding to solution GR8) also show similar features asshown in FIG. 43Q.

Thus, these TEM photomicrographs suggest that the processing parametersutilized to manufacture GR5 resulted in somewhat smaller silver-basednanoparticles, when compared to those silver-based nanoparticlesassociated with GR8. The primary difference in production parametersbetween GR5 and GR8 was the location of the two adjustable plasmas 4used to make the silver constituents in each solution. The zincconstituents in both of GR5 and GR8 are the same. However, the silverconstituents in GR5 is made by adjustable plasmas 4 located at the FirstElectrode Set and the Fourth Electrode Set; whereas the silverconstituent in GR8 is made by adjustable plasmas 4 located at the Firstand Second Electrode Sets.

UV-VIS Spectroscopy

Energy absorption spectra were obtained using US-VISmicro-spec-photometry. This information was acquired using dual beamscanning monochrometer systems capable of scanning the wavelength rangeof 190 nm to 1100 nm. Two UV-Vis spectrometers were used to collectabsorption spectra; these were a Jasco V530 and a Jasco MSV350.Instrumentation was setup to support measurement of low-concentrationliquid samples using one of a number of fuzed-quartz sample holders or“cuvettes”. The various cuvettes allow data to be collected at 10 mm, 1mm or 0.1 mm optic path of sample. Data was acquired over the abovewavelength range using both PMT and LED detectors with the followingparameters; bandwidth of 2 nm, with data pitch of 0.5 nm, with andwithout a water baseline background. Both tungsten “halogen” andHydrogen “D2” energy sources were used as the primary energy sources.Optical paths of these spectrometers were setup to allow the energy beamto pass through the samples with focus towards the center of the samplecuvettes. Sample preparation was limited to filling and capping thecuvettes and then physically placing the samples into the cuvetteholder, within the fully enclosed sample compartment. Optical absorptionof energy by the materials of interest was determined. Data output wasmeasured and displayed as Absorbance Units (per Beer-Lambert's Law)versus wavelength and frequency.

Spectral signatures in a UV-Visible range were obtained for each of theraw materials produced in Examples 1-5 as well as in each of thesolutions GR1-GR10 shown in Tables 8 and 9.

Specifically, FIG. 44A shows UV-Vis spectral signature of each of the 5raw materials with a wavelength of about 190 nm-600 nm.

FIG. 44B shows the UV-Vis spectral pattern for each of the 10 solutionsGR1-GR10 for the same wavelength range.

FIG. 44C shows the UV-Vis spectral pattern of each of the 10 solutionsGR1-GR10 over a range of 190 nm-225 nm.

FIG. 44D is a UV-Vis spectra of each of the 10 solutions GR1-GR10 over awavelength of about 240 nm-500 nm.

FIG. 44E is a UV-Vis spectral pattern for each of the solutions GR1-GR10over a wavelength range of about 245 nm-450 nm.

The UV-Vis spectral data for each of FIGS. 44A-44E were obtained from aJasco V-530 UV-Vis Spectrophotometer. Pertinent operational conditionsfor the collection of each UV-Vis spectral pattern are shown in FIGS.44A-44E.

In general, UV-Vis spectroscopy is the measurement of the wavelength andintensity of absorption of near-ultraviolet and visible light by asample. Ultraviolet and visible light are energetic enough to promoteouter electrons to higher energy levels. UV-Vis spectroscopy can beapplied to molecules and inorganic ions or complexes in solution.

The UV-Vis spectra have broad features that can be used for sampleidentification but are also useful for quantitative measurements. Theconcentration of an analyte in solution can be determined by measuringthe absorbance at some wavelength and applying the Beer-Lambert Law.

The dual beam UV-Vis spectrophotometer was used to subtract any signalsfrom the solvent (in this case water) in order to specificallycharacterize the samples of interest. In this case the reference is thefeedstock water that has been drawn from the outlet of the ReverseOsmosis process discussed in the Examples section herein.

Raman Spectroscopy

Raman spectral signatures were obtained using a Renishaw InviaSpectrometer with relevant operating information shown in FIG. 45. Itshould be noted that no significant differences were seen for each ofthe GR1-GR10 blends using Raman Spectroscopy.

The reflection micro-spectrograph with Leica DL DM microscope was fittedwith either a 20× (NA=0.5) water immersion or a 5× (NA=0.12) dry lens.The rear aperture of each lens was sized to equal or exceed the expandedlaser beam diameter. Two laser frequencies were used, these being amultiline 50 mW Argon laser at ½ power setup for 514.5 nm and a 20 mWHeNe laser at 633 nm. High resolution gratings were fitted in themonochrometer optic path which allowed continuous scans from 50 to 4000wavenumbers (1/cm). Ten to 20 second integration times were used. Samplefluid was placed below the lens in a 50 ml beaker. Both lasers were usedto investigate resonance bands, while the former laser was primarilyused to obtain Raman spectra. Sample size was about 25 ml. Measurementsmade with the 5× dry lens were made with the objective positioned about5 mm above the fluid to interrogate a volume about 7 mm beneath thewater meniscus. Immersion measurements were made with the 20× immersionlens positioned about 4 mm into the sample allowing investigation of thesame spatial volume. CCD detector acquisition areas were individuallyadjusted for each lens to maximize signal intensity and signal-to-noiseratios.

Biological Characterization Bioscreen Results

A Bioscreen C microbiology reader was utilized to compare theeffectiveness of the raw materials made in accordance with Examples 1-5,as well as the 10 solutions GR1-GR10 made therefrom. Specific procedurefor obtaining Bioscreen results follows below.

Bacterial Strains

Escherichia coli was obtained from the American Type Culture Collection(ATCC) under the accession number 25922. The initial pellets werereconstituted in trypticase soy broth (TSB, Becton Dickinson andCompany, Sparks, Md.) and aseptically transferred to a culture flaskcontaining 10 ml of TSB followed by overnight incubation at 37° C. in aForma 3157 water-jacketed incubator (Thermo Scientific, Waltham, Mass.,USA).

Maintenance and Storage of Bacteria

Bacterial strains were kept on trypticase soy agar (TSA, BectonDickinson and Company, Sparks, Md.) plates and aliquots werecryogenically stored at −80° C. in MicroBank tubes (Pro-LabIncorporated, Ontario, Canada).

Preparation of Bacterial Cultures

Microbank tubes were thawed at room temperature and opened in a NuAireLabgard 440 biological class II safety cabinet (NuAire Inc., Plymouth,Minn., USA). Using a sterile inoculating needle, one microbank bead wasaseptically transferred from the stock tube into 10 ml of eitherTrypticase Soy Broth (TSB, Becton Dickenson and Company, Sparks, Md.)for Bioscreen analysis or Mueller-Hinton Broth (MHB, Becton Dickinsonand Company, Sparks, Md.) for MIC/MLC analysis. Overnight cultures ofbacterial strains were grown at 37° C. for 18 hours in a Forma 3157water-jacketed incubator (Thermo Scientific, Waltham, Mass., USA) anddiluted to a 0.5 McFarland turbidity standard. Subsequently, a 10⁻¹dilution of the McFarland standard was performed, to give an approximatebacterial count of 1.0×10⁷ CFU/ml. This final dilution must be usedwithin 30 minutes of creation to prevent an increase in bacterialdensity due to cellular growth.

Dilution of Nanoparticle Solutions

Nanoparticle solutions were diluted in MHB and sterile dH₂O to a 2×testing concentration yielding a total volume of 1.5 ml. Of this volume,750 μl consisted of MHB, while the other 750 μl consisted of varyingamounts of sterile dH₂O and the nanoparticle solution to make a 2×concentration of the particular nanoparticle solution being tested.Testing dilutions (final concentration in reaction) ranged from 0.5 ppmAg to 6.0 ppm Ag nanoparticle concentration with testing performed atevery 0.5 ppm interval.

Preparation of Bioscreen Reaction

To determine the minimum inhibitory concentration (MIC) of nanoparticlesolutions, 100 μl of the diluted bacterial culture was added to 100 μlof a particular nanoparticle solution at the desired testingconcentration in the separate, sterile wells of a 100 well microtiterplate (Growth Curves USA, Piscataway, N.J., USA). Wells inoculated withboth 100 μl of the diluted bacterial culture and 100 μl of a 1:1MHB/sterile ddH₂O mix served as positive controls, while wells with 100μl of MHB and 100 μl of a 1:1 MHB/sterile ddH₂O mix served as negativecontrols for the reaction. Plates were placed inside the tray of aBioscreen C Microbiology Reader (Growth Curves USA, Piscataway, N.J.,USA) and incubated at a constant 37° C. for 15 hours with opticaldensity (O.D.) measurements being taken every 10 minutes. Before eachO.D. measurement, plates were automatically shaken for 10 seconds atmedium intensity to prevent settling of bacteria and to ensure ahomogenous reaction well.

Determination of Both MIC and MLC

All data was collected using EZExperiment Software (Growth Curves USA,Piscataway, N.J., USA) and analyzed using Microsoft Excel (MicrosoftCorporation, Redmond, Wash., USA). The growth curves of bacteria strainstreated with different nanoparticle solutions were constructed and theMIC determined. The MIC was defined as the lowest concentration ofnanoparticle solution that prevented the growth of the bacterial culturefor 15 hours, as measured by optical density using the Bioscreen CMicrobiology Reader.

Once the MIC was determined, the test medium from the MIC and subsequenthigher concentrations was removed from each well and combined accordingto concentration in appropriately labeled, sterile Eppendorf tubes. TSAplates were inoculated with 100 μl of test medium and incubatedovernight at 37° C. in a Forma 3157 water-jacketed incubator (ThermoScientific, Waltham, Mass., USA). The minimum lethal concentration (MLC)was defined as the lowest concentration of nanoparticle solution thatprevented the growth of the bacterial culture as measured by colonygrowth on TSA.

The results of the Bioscreen runs are shown in FIG. 46. It should benoted that the raw materials AT031; AT059 and AT060 had reasonableperformance, whereas the raw materials BT-006 and CT-006 did not slowdown growth of the E. coli at all. In this regard, the longer a curveremains at low optical density (“OD”) the better the performance againstbacteria.

In contrast, each of the solutions GR1-GR10 showed superior performance,relative to each of the raw materials AT031, AT060 and AT059.Interestingly, the combination of the raw materials associated withsilver nanoparticles with those raw materials associated with both zincand copper nanoparticles produced unexpected synergistic results.

Additional Bioscreen results are shown in FIGS. 47 and 48. Data reportedin these FIGs. are known as “MIC” data. “MIC” stands for minimuminhibitory concentration. MIC data was only generated for GR3 and GR8.It is clear from reviewing the data in each of FIGS. 47 and 48 thatappropriate MIC values for GR3 and GR8 were around 2-3 ppm

Due to the unexpected favorable results shown in FIG. 46, the sequentialaddition of the raw material BT-006, made in accordance with Example 4,was added to the raw material AT-060 made in accordance with Example 2(i.e., a zinc-based nanoparticle solution was added to a silver-basednanoparticle solution. The amount of silver present (as determined byatomic absorption spectroscopy) was maintained at 1 ppm. The amount ofBT-006 in the nanoparticle solution added thereto is reported in FIG.49. It is interesting to note that enhanced antimicrobial performanceagainst E. coli was achieved with increasing amounts of zincnanoparticle solutions, i.e., BT-006, (from Example 4) being addedthereto. Further, FIGS. 50A-50D show additional Bioscreen informationshowing performance against E. coli by adding a conditioned water(“GZA”) to the nanoparticle solution AT-060 from Example 2.

GZA raw material was made in a manner similar to the BT-006 raw materialexcept that a platinum electrode 1/5 configuration was utilized ratherthan zinc.

Freeze-Drying

FIG. 54 shows another set of Bioscreen results whereby solutionsreferred to in Tables 8 and 9 herein as GR5 and GR8, were compared forefficacy against E. coli, as well as the same solutions having beenfirst completely freeze-dried and thereafter rehydrated with water(liquid 3) such rehydration being effected to result in the sameoriginal ppm.

Freeze-drying was accomplished by placing the GR5 and GR8 solution in aplastic (nalgene) container and placing the plastic container in aBenchTop 2K freeze dryer (manufactured by Virtis) which was maintainedat a temperature of about −52° C. and a vacuum of less than 100milliliter. About 10-20 ml of solution will freeze-dry overnight.

As is shown in FIG. 54s , the performance of freeze-dried and rehydratednanoparticles is identical to the performance of the original GR5 andGR8 solutions.

Viability/Cytoxicity Testing of Mammalian Cells

The following procedures were utilized to obtain cell viability and/orcytotoxicity measurements.

Cell Lines

Mus musculus (mouse) liver epithelial cells (accession number CRL-1638)and Sus scrofa domesticus (minipig) kidney fibrobast cells (accessionnumber CCL-166) were obtained from the American Type Culture Collection(ATCC).

Cell Culturing from Frozen Stocks

Cell lines were thawed by gentle agitation in a Napco 203 water bath(Thermo Scientific, Waltham, Mass., USA) at 37° C. for 2 minutes. Toreduce microbial contamination, the cap and O-ring of the frozen culturevial were kept above the water level during thawing. As soon as thecontents of the culture vial were thawed, the vial was removed from thewater, sprayed with 95% ethanol, and transferred into a NuAire Labgard440 biological class II safety cabinet (NuAire Inc., Plymouth, Minn.,USA). The vial contents were then transferred to a sterile 75 cm² tissueculture flask (Corning Life Sciences, Lowell, Mass., USA) and dilutedwith the recommended amount of complete culture medium. Murine liverepithelial cell line CRL-1638 required propagation in complete culturemedia composed of 90% Dulbecco's Modified Eagle's Medium (ATCC,Manassas, Va., USA) and 10% fetal bovine serum (ATCC, Manassas, Va.,USA), while minipig kidney fibroblast cell line CCL-166 was grown incomplete culture media comprised of 80% Dulbecco's Modified Eagle'sMedium and 20% fetal bovine serum. Cell line CRL-1638 was diluted withgrowth media in a 1:15 ratio, while cell line CCL-166 was diluted withgrowth media in a 1:10 ratio. The culture flasks were then incubated atabout 37° C., utilizing a 5% CO₂ and 95% humidified atmosphere in aNuAire, IR Autoflow water-jacketed, CO₂ incubator (NuAire Inc.,Plymouth, Minn., USA).

Medium Renewal and Care of Growing Cells

Every two days, old growth medium was removed from culturing flasks andreplaced with fresh growth medium. Each day, observations for microbialgrowth, such as fungal colonies and turbidity in medium, were made withthe naked eye. Additionally, cultured cells were observed under aninverted phase contrast microscope (VWR Vistavision, VWR International,and West Chester, Pa., USA) to check for both general health of thecells and cell confluency.

Subculturing of Cells

Once cells reached approximately 80% confluent growth, cells were deemedready for subculturing. Old growth medium was removed and discarded andthe cell sheet rinsed with 5 ml of prewarmed trypsin-EDTA dissociatingsolution (ATCC, Manassas, Va., USA). After 30 seconds of contact withthe cell sheet, the trypsin-EDTA was removed and discarded. Ensuringthat both the entire cell monolayer was covered and the flask was notagitated, a 3 ml volume of the prewarmed trypsin-EDTA solution was addedto the cell sheet followed by incubation of the culture flask at 37° C.for about 15 minutes. After cell dissociation, trypsin-EDTA wasinactivated by adding about 6 ml of complete growth medium to the cellculture flask followed by gentle pipetting to aspirate cells.

In order to count cells, 200 μl of the cell suspension was collected ina 15 ml centrifuge tube (Corning Life Sciences, Lowell, Mass., USA).Both 300 μL of phosphate buffered saline (ATCC, Manassas, Va., USA) and500 μL of a 0.4% trypan blue solution (ATCC, Manassas, Va., USA) wasadded to the collected cell suspension and mixed thoroughly. Afterallowing to stand for about 15 minutes, 10 μl of the mixture was placedin each chamber of an iN Cyto, C-Chip disposable hemacytometer (INCYTO,Seoul, Korea) where the cells were counted with a VWR Vistavisioninverted phase contrast microscope (VWR International, West Chester,Pa., USA) according to the manufacturer's instructions. Theconcentration of the cells in the suspension was calculated using aconversion formula based upon the cell count obtained from thehemacytometer.

Cytotoxicity Testing

The wells of black, clear bottom, cell culture-treated microtiter plates(Corning Life Sciences, Lowell, Mass., USA) were seeded with 200 μl ofculture medium containing approximately 1.7×10⁴ cells as shown inFIG. 1. Cells were allowed to equilibrate in the microtiter plates atabout 37° C., utilizing a 5% CO₂ and 95% humidified atmosphere for about48 hours. After the equilibration period, culture medium was removedfrom each well and replaced with 100 μl of fresh growth medium in allwells except for those in column 3 of the plate. A 100 μl volume offresh medium supplemented with 2× of the desired testing concentrationof each solution was placed in each well as shown in Table 10.

Table 10

Table 10. Microwell plate setup for cytotoxicity testing. All outerwells (shaded area) of the plate contained only 200 μl of culture medium(no cells) to act as a blank vehicle control (VCb) for the experiment.As a positive vehicle control, wells 2B-2G (VC1) and wells 11B-11G (VC2)were seeded with both culture medium and cells. One solution was testedon each plate (H_(x)). The highest concentration of solution was placedin wells 3B-3D (C₁), while seven, 20% dilutions (C₂-C₇) of each solutionwere present in each consecutive well.

Microtiter plates were incubated with the treatment compounds 37° C.,utilizing a 5% CO₂ and 95% humidified atmosphere for 24 hours. Afterincubation with nanoparticle solutions, the culture medium was removedand discarded from each well and replaced with 100 μl of fresh mediacontaining Alamar Blue™ (Biosource International, Camarillo, Calif.,USA) at a concentration of 50 μl dye/ml media. Plates were gently shakenby hand for about 10 seconds and incubated at about 37° C., utilizing a5% CO₂ and 95% humidified atmosphere for 2.5 hours. Fluorescence wasthen measured in each well utilizing an excitation wavelength of 544 nmand an emission wavelength of 590 nm. Fluorescence measurements werecarried out on the Fluoroskan II fluorometer produced by Labsystems(Thermo Scientific, Waltham, Mass., USA).

Data Analysis

Cytotoxicity of the nanoparticle solutions was determined by measuringthe proportion of viable cells after treatment when compared to thenon-treated control cells. A percent viability of cells after treatmentwas then calculated and used to generate the concentration ofnanoparticle at which fifty percent of cellular death occurred (LC₅₀).All data was analyzed using GraphPad Prism software (GraphPad SoftwareInc., San Diego, Calif., USA).

Results of the viability/cytotoxicity tests are shown in FIGS. 51A-51H;52A-52F; and FIGS. 53A-53H.

With regard to FIGS. 51A and 51B, the performance of solution “GR3” wastested against both mini-pig kidney fibroblast cells (FIG. 51A) andmurine liver epithelial cells (FIG. 51B).

Similarly, FIGS. 51C and 51D tested the performance of GR5 againstkidney cells and murine liver cells, respectively; FIGS. 51E and 51Ftested the performance of GR8 against kidney cells and liver cells,respectively; and FIGS. 51G and 51H tested the performance of GR9against kidney cells and liver cells, respectively.

In each of FIGS. 51A-51H, a biphasic response is noted. A biphasicresponse occurred at different concentrations for each solution and setof cells, however, the general trend or each solution tested showed thata certain concentration of nanoparticles produced according to theembodiments disclosed herein exhibited enhanced growth rates for each ofthe kidney and liver cells, relative to control. In this regard, anyportion of any of the curves that are vertically above the dotted linecorresponding to 100% (i.e., control) had a higher flourometer readingfrom the generated flourenscence discussed above herein. Accordingly, itis clear that particles and/or nanoparticle solutions made according tothe present invention can have an enhanced growth rate effect onmammalian cells including at least, kidney and liver cells.

FIGS. 52A-52F tested a narrower response range of both silvernanoparticle concentrations and total nanoparticle concentrations. Thevalues “LD₅₀” reported for each of the solutions 3, 5 and 8 in each ofFIGS. 52AB, 52CD, and 52EF, respectively, correspond to the parts permillion of silver-based nanoparticles (FIGS. 52A, C and E) and totalnanoparticle parts per million (corresponding to FIGS. 52B, D and F).With regard to the silver nanoparticle concentration, it is clear thatLD₅₀'s range between about 2.5 to about 5.4. In contrast, the LD₅₀'s forthe total nanoparticle solutions vary from about 6 to about 16.

With regard to FIG. 53A-53H, “LD₅₀” measurements were made for eachsolution GR3, GR5, GR8 and GR9 against mini-pig kidney fibroblast cells.As shown in each of these FIGs., the “LD₅₀” values for totalnanoparticles present ranged from a low of about 4.3 for GR9 to a highof about 10.5-11 for each of GR5 and GR8.

Example 6 Manufacturing Silver-Based Nanoparticles/NanoparticleSolutions AT098, AT099 and AT100 without the Use of any Plasmas

This Example utilizes the same basic apparatus used to make thesolutions of Examples 1-5. However, this Example does not utilize anyelectrode(s) 1. This Example utilizes 99.95% pure silver electrodes foreach electrode 5. Tables 11a, 11b and 11c summarize portions ofelectrode design, configuration, location and operating voltages. Asshown in Tables 11a, 11b and 11c, the target voltages were set to a lowof about 2,750 volts in Electrode Set #8 and to a high of about 4,500volts in Electrode Sets #1-3. The high of 4,500 volts essentiallycorresponds to an open circuit which is due to the minimal conductivityof the liquid 3 between each electrode 5, 5′ in Electrode Sets #1-3

Further, bar charts of the actual and target voltages for each electrodein each electrode set, are shown in FIGS. 55A, 55B and 55C. Accordingly,the data contained in Tables 11a, 11b and 11c, as well as FIGS. 55A, 55Band 55C, give a complete understanding of the electrode design in eachelectrode set as well as the target and actual voltages applied to eachelectrode for the inventive manufacturing process. To maintainconsistency with the reported electrode configurations of Examples 1-5,space for eight sets of electrodes have been included in each of Tables11a, 11b and 11c, even though Run ID “AT100” was the only run thatactually used eight sets of electrodes.

TABLE 11a Run ID: AT098 Flow Rate: 200 ml/min Target Average VoltageDistance Distance Voltage Set # Electrode # (kV) “c-c” in/mm “x” in/mm(kV)  7/177.8* 1 5a 4.54 N/A 4.54 5a′ 4.52 N/A 4.51 65/1651** N/A N/AN/A N/A N/A N/A N/A Output Water 24 C. Temperature *Distance from waterinlet to center of first electrode set **Distance from center of lastelectrode set to water outlet

TABLE 11b Run ID: AT099 Flow Rate: 200 ml/min Target Average VoltageDistance Distance Voltage Set # Electrode # (kV) “c-c” in/mm “x” in/mm(kV)  7/177.8* 1 5a 4.54 N/A 4.53 5a′ 4.52 N/A 4.49 8/203.2 2 5b 4.55N/A 4.56 5b′ 4.51 N/A 4.52  57/1447.8** N/A N/A N/A N/A N/A N/A OutputWater 24 C. Temperature *Distance from water inlet to center of firstelectrode set **Distance from center of last electrode set to wateroutlet

TABLE 11c Run ID: AT100 Flow Rate: 200 ml/min Target Average VoltageDistance Distance Voltage Set # Electrode # (kV) “c-c” in/mm “x” in/mm(kV)  7/177.8* 1 5a 4.53 N/A 4.53 5a′ 4.49 N/A 4.49 8/203.2 2 5b 4.51N/A 4.51 5b′ 4.48 N/A 4.47 8/203.2 3 5c 4.52 N/A 4.52 5c′ 4.45 N/A 4.458/203.2 4 5d 4.40 N/A 4.40 5d′ 4.32 N/A 4.32 9/228.6 5 5e 4.38 N/A 4.375e′ 4.27 N/A 4.26 8/203.2 6 5f 3.85 N/A 3.80 5f′ 3.71 N/A 3.65 8/203.2 75g 3.55 N/A 3.43 5g′ 3.30 N/A 3.23 8/203.2 8 5h 2.79 N/A 2.76 5h′ 2.75N/A 2.69  8/203.2** Output Water 82 C. Temperature *Distance from waterinlet to center of first electrode set **Distance from center of lastelectrode set to water outlet

Atomic Absorption Spectroscopy (AAS) samples were prepared andmeasurement values were obtained. Slight process modifications wereincorporated into those AAS procedures discussed earlier herein. Theseprocess changes are incorporated immediately below.

The AAS values were obtained from a Perkin Elmer AAnalyst 300Spectrometer system, as in Examples 1-5. The samples manufactured inaccordance with Examples 6-12 were prepared by adding a small amount ofnitric acid or hydrochloric acid (usually 2-4% of final volume) and thendilution to a desirable characteristic concentration range or linearrange of the specific element to improve accuracy of the result. The“desireable” range is an order of magnitude estimate based on productionparameters established during product development. For pure metalsanalysis, a known amount of feedstock material is digested in a knownamount of acid and diluted to ensure that the signal strength of theabsorbance will be within the tolerance limits and more specifically themost accurate range of the detector settings, better known as the linearrange.

The specific operating procedure for the Perkin Elmer AAnalyst 300system is as follows:

I) Principle

-   -   The Perkin Elmer AAnalyst 300 system consists of a high        efficiency burner system with either a sapphire GemTip or        stainless steel beaded nebulizer and an atomic absorption        spectrometer. The burner system provides the thermal energy        necessary to dissociate the chemical compounds, providing free        analyte atoms so that atomic absorption occurs. The spectrometer        measures the amount of light absorbed at a specific wavelength        using a hollow cathode lamp as the primary light source, a        monochromator and a detector. A deuterium arc lamp corrects for        background absorbance caused by non-atomic species in the atom        cloud.

II) Instrument Setup

-   -   A) Empty waste container to mark. Add deionized water to drain        tubing to ensure that water is present in the drain system float        assembly.    -   B) Ensure that the appropriate Hollow Cathode Lamp for the        analyte to be analyzed is properly installed in the turret.    -   C) Power AAnalyst 300 and computer ON.    -   D) After the AAnalyst 300 has warmed up for a minimum of 30        minutes, start the AAWin Analyst software    -   E) Recall Method to be analyzed.    -   F) Ensure that the correct Default Conditions are entered.    -   G) Align the Hollow Cathode Lamp.        -   1) Allow HCL's to warm and stabilize for a minimum of 15            minutes.        -   2) Check that a proper peak and energy level has been            established for the specific lamp.        -   3) Adjust the power and frequency of the lamp settings to            obtain maximum energy.    -   H) Store Method changes in Parameter Entry, Option, Store and #.    -   I) Adjust Burner height.        -   1) Place a white sheet of paper behind the burner to confirm            the location of the light beam.        -   2) Lower the burner head below the light beam with the            vertical adjustment knob.        -   3) Press Cont (Continuous) to display an absorbance value.        -   4) Press A/Z to Autozero.        -   5) Raise the burner head with the vertical adjustment knob            until the display indicates a slight absorbance (0.002).            Slowly lower the head until the display returns to zero.            Lower the head an additional quarter turn to complete the            adjustment.    -   J) Ignite flame.        -   1) Open air compressor valve. Set pressure to 50 to 65 psi.        -   2) Open acetylene gas cylinder valve. Set output pressure to            12 to 14 psi. Replace cylinder when pressure falls to 75 psi            to prevent valve and tubing damage from the presence of            acetone.        -   3) Press Gases On/Off. Adjust oxidant flow to 4 Units.        -   4) Press Gases On/Off. Adjust acetylene gas flow to 2 Units.        -   5) Press Flame On/Off to turn flame on.            -   Note: Do not directly view the lamp or flame without                protective ultraviolet radiation eyewear.    -   K) Aspirate deionized water through the burner head to fully        warm the burner head for 3 to 5 minutes.    -   L) Adjust Burner Position and Nebulizer.        -   1) Aspirate a standard with a signal of approximately            0.2-0.5 absorbance units.        -   2) Obtain maximum burner position absorbance by rotating the            horizontal, vertical and rotational adjustment knobs.        -   3) Loosen the nebulizer locking ring by turning it            clockwise. Slowly turn the nebulizer adjustment knob to            obtain maximum absorbance. Lock the knob in place with the            locking ring.        -   Note: An element, such as Silver, which is at a wavelength            where gases do not absorb is optimal for adjusting the            Burner and Nebulizer.

III) Calibration Procedure

-   -   A) Calibrate with standards that bracket the sample        concentrations.    -   B) WinAA Analyst software will automatically create a        calibration curve for your sample readings. But check to ensure        that proper absorption is established with each calibration        standard.    -   C) Enter Standard Concentration Values in the Default Conditions        to calculate an AAnalyst 300 standard curve.        -   1) Enter the concentration of the lowest standard for STD1            using significant digits.        -   2) Enter the concentrations of the other standards of the            calibration curve in ascending order and the concentration            of the reslope standard.        -   3) Autozero with the blank before acquiring calibration            values.        -   4) Aspirate Standard 1, press 0 Calibrate to clear the            previous curve. Aspirate the standards in numerical order.        -   Press standard number and calibrate for each standard.        -   5) Press Print to print the graph and correlation            coefficient.        -   6) Rerun one or all standards, if necessary. To rerun            Standard 3, aspirate standard and press 3 Calibrate.    -   D) The correlation coefficient should be greater than or equal        to 0.990.    -   E) Check the calibration curve for drift, accuracy and precision        with calibration standards continuously during operation, at        minimum, one every 20 samples.

IV) Analysis Procedure

-   -   A) Samples are measured in triplicate using a minimum of 3        replicates per sample.    -   B) Aspirate sample and press Read Sample. The software will take        3 readings of absorbance and then average those readings. Wait        until software says idle. Rerun the sample if the standard        deviation is greater than 50% of the sample result.

V) Instrument Shutdown

-   -   A) Aspirate 2% Nitric Acid (HNO₃) for 1-3 minutes and deionized        water for 3-5 minutes to clean the burner head. Remove the        capillary tube from the water and run burner-head dry for about        1 minute.    -   B) Press Flame On/Off to turn off flame.    -   C) Close air compressor valve.    -   D) Close acetylene cylinder valve.    -   E) Press Bleed Gases to bleed the acetylene gas from the lines.        The cylinder pressure should drop to zero.    -   F) Exit the software, power OFF the AAnalyst 300, and shut down        the computer.

TABLE 11d Run ID Electrode Configuration Measured PPM AT098 0XXXXXXXBelow Detectable Limit AT099 00XXXXXX Less Than 0.2 PPM AT100 000000007.1 PPM

Table 11d shows the results obtained from Example 6. Table 11d containsa column entitled “Electrode Configuration”. This column containscharacters “0” and “X”. The character “0” corresponds to one electrodeset 5, 5′. The character “X” represents that no electrodes were present.Thus, for Run ID “AT098”, only a single electrode set 5 a, 5 a′ wasutilized. No detectable amount of silver was measurable by the AAStechniques disclosed herein. Run ID “AT099” utilized two electrode sets5 a, 5 a′ and 5 b, 5 b′. The AAS techniques detected some amount ofsilver as being present, but that amount was less than 0.2 ppm. Run ID“AT100” utilized eight electrode sets, 5, 5′. This configurationresulted in a measured ppm of 7.1 ppm. Accordingly, it is possible toobtain metallic-based constituents (e.g., metallic-basednanoparticles/nanoparticle solution) without the use of an electrode 1(and an associated adjustable plasma 4). However, the rate of formationof metallic-based constituents is much less than that rate obtained byusing one or more plasmas 4. For example, Examples 1-3 disclosedsilver-based products associated with Run ID's AT031, AT036 and AT038.Each of those Run ID's utilized two electrode sets that includedadjustable plasmas 4. The measured silver ppm for each of these sampleswas greater than 40 ppm, which is 5-6 times more than what was measuredin the product made according to Run ID AT100 in this Example 6. Thus,while it is possible to manufacture metallic-based constituents withoutthe use of at least one adjustable plasma 4 (according to the teachingsherein) the rates of formation of metallic based constituents aregreatly reduced when no plasmas 4 are utilized as part of the productiontechniques.

Accordingly, even though eight electrode sets 5, 5′ were utilized tomake the product associated with Run AT100, the lack of any electrodesets including at least one electrode 1 (i.e., the lack of plasma 4),severely limited the ppm content of silver in the solution produced.

Example 7 Manufacturing Silver-Based Nanoparticles/NanoparticleSolutions AT080, AT081, AT082, AT083, AT084, AT085, AT086 and AT097Using Only a Single Plasma

This Example utilizes the same basic apparatus used to make thesolutions of Examples 1-5, however, this Example uses only a singleplasma 4. Specifically, for Electrode Set #1, this Example uses a “1 a,5 a” electrode configuration. Subsequent Electrode Sets #2-#8 aresequentially added. Each of Electrode Sets #2-#8 have a “5, 5′”electrode configuration. This Example also utilizes 99.95% pure silverelectrodes for each of electrodes 1 and 5 in each Electrode Set.

Tables 12a-12h summarize portions of electrode design, configuration,location and operating voltages. As shown in Tables 12a-12h, the targetvoltages were set to a low of about 900 volts (at Electrode Set #8) anda high of about 2,300 volts (at Electrode Set #1).

Further, bar charts of the actual and target voltages for each electrodein each electrode set, are shown in FIGS. 56A, 56B, 56C, 56D, 56E, 56F,56G and 56H. Accordingly, the data contained in Tables 12a-12h, as wellas FIGS. 56A, 56B, 56C, 56D, 56E, 56F, 56G and 56H, give a completeunderstanding of the electrode design in each electrode set as well asthe target and actual voltages applied to each electrode for themanufacturing processes. To maintain consistency with the reportedelectrode configurations of Examples 1-5, space for eight sets ofelectrodes have been included in each in each of Tables 12a, 12b, 12c,12d, 12e, 12f, 12g and 12h even though Run ID “AT080” was the only runthat actually used eight sets of electrodes.

TABLE 12a Run ID: AT097 Flow Rate: 200 ml/min Target Average VoltageDistance Distance Voltage Set # Electrode # (kV) “c-c” in/mm “x” in/mm(kV)  7/177.8* 1 1a 1.78 .26/6.8 1.79 5a 1.82 N/A 1.79 65/1651** N/A N/AN/A N/A N/A N/A N/A Output Water 35 C. Temperature *Distance from waterinlet to center of first electrode set **Distance from center of lastelectrode set to water outlet

TABLE 12b Run ID: AT086 Flow Rate: 200 ml/min Target Average VoltageDistance Distance Voltage Set # Electrode # (kV) “c-c” in/mm “x” in/mm(kV)  7/177.8* 1 1a 2.18 .26/6.8 2.15 5a 1.63 N/A 1.67 8/203.2 2 5b 1.05N/A 1.05 5b′ 1.39 N/A 1.43  57/1447.8** N/A N/A N/A N/A N/A N/A OutputWater 38 C. Temperature *Distance from water inlet to center of firstelectrode set **Distance from center of last electrode set to wateroutlet

TABLE 12c Run ID: AT085 Flow Rate: 200 ml/min Target Average VoltageDistance Distance Voltage Set # Electrode # (kV) “c-c” in/mm “x” in/mm(kV)  7/177.8* 1 1a 2.24 .26/6.8 2.19 5a 1.79 N/A 1.79 8/203.2 2 5b 1.16N/A 1.16 5b′ 1.24 N/A 1.23 8/203.2 3 5c 1.12 N/A 1.14 5c′ 1.34 N/A 1.35 49/1244.6** N/A N/A N/A N/A N/A Output Water 43 C. Temperature*Distance from water inlet to center of first electrode set **Distancefrom center of last electrode set to water outlet

TABLE 12d Run ID: AT084 Flow Rate: 200 ml/min Target Average VoltageDistance Distance Voltage Set # Electrode # (kV) “c-c” in/mm “x” in/mm(kV)  7/177.8* 1 1a 2.29 .26/6.8 2.25 5a 1.95 N/A 1.94 8/203.2 2 5b 1.27N/A 1.26 5b′ 1.39 N/A 1.39 8/203.2 3 5c 1.35 N/A 1.34 5c′ 1.26 N/A 1.258/203.2 4 5d 1.31 N/A 1.32 5d′ 1.59 N/A 1.56  41/1041.4** N/A N/A N/AN/A Output Water 49 C. Temperature *Distance from water inlet to centerof first electrode set **Distance from center of last electrode set towater outlet

TABLE 12e Run ID: AT083 Flow Rate: 200 ml/min Target Distance AverageVoltage “c-c” Distance Voltage Set # Electrode # (kV) in/mm “x” in/mm(kV)  7/177.8* 1 1a 2.17 .26/6.8 2.16 5a 1.72 N/A 1.74 8/203.2 2 5b 1.10N/A 1.12 5b′ 1.32 N/A 1.34 8/203.2 3 5c 1.25 N/A 1.24 5c′ 1.12 N/A 1.138/203.2 4 5d 1.31 N/A 1.29 5d′ 1.32 N/A 1.33 9/228.6 5 5e 1.63 N/A 1.645e′ 1.52 N/A 1.52  32/812.8** N/A N/A N/A Output Water 56 C. Temperature*Distance from water inlet to center of first electrode set **Distancefrom center of last electrode set to water outlet

TABLE 12f Run ID: AT082 Flow Rate: 200 ml/min Target Distance AverageVoltage “c-c” Distance Voltage Set # Electrode # (kV) in/mm “x” in/mm(kV)  7/177.8* 1 1a 2.18 .26/6.8 2.17 5a 1.76 N/A 1.75 8/203.2 2 5b 1.08N/A 1.09 5b′ 1.31 N/A 1.32 8/203.2 3 5c 1.26 N/A 1.26 5c′ 1.09 N/A 1.088/203.2 4 5d 1.28 N/A 1.27 5d′ 1.25 N/A 1.22 9/228.6 5 5e 1.60 N/A 1.605e′ 1.17 N/A 1.17 8/203.2 6 5f 0.99 N/A 0.98 5f′ 1.19 N/A 1.18 24/609.6** N/A N/A Output Water 63 C. Temperature *Distance from waterinlet to center of first electrode set **Distance from center of lastelectrode set to water outlet

TABLE 12g Run ID: AT081 Flow Rate: 200 ml/min Target Distance DistanceAverage Voltage “c-c” “x” Voltage Set # Electrode # (kV) in/mm in/mm(kV)  7/177.8* 1 1a 2.23 .26/6.8 2.18 5a 1.77 N/A 1.79 8/203.2 2 5b 1.09N/A 1.09  5b′ 1.30 N/A 1.28 8/203.2 3 5c 1.22 N/A 1.21  5c′ 1.07 N/A1.07 8/203.2 4 5d 1.27 N/A 1.27  5d′ 1.21 N/A 1.21 9/228.6 5 5e 1.60 N/A1.58  5e′ 1.26 N/A 1.23 8/203.2 6 5f 1.10 N/A 1.09  5f′ 1.02 N/A 0.998/203.2 7 5g 1.14 N/A 1.11  5g′ 1.34 N/A 1.32  16/406.4** N/A OutputWater Temperature 72 C. *Distance from water inlet to center of firstelectrode set **Distance from center of last electrode set to wateroutlet

TABLE 12h Run ID: AT080 Flow Rate: 200 ml/min Target Distance DistanceAverage Voltage “c-c” “x” Voltage Set # Electrode # (kV) in/mm in/mm(kV)  7/177.8* 1 1a 2.11 .26/6.8 2.13 5a 1.72 N/A 1.73 8/203.2 2 5b 1.00N/A 1.00  5b′ 1.23 N/A 1.24 8/203.2 3 5c 1.16 N/A 1.16  5c′ 0.97 N/A0.98 8/203.2 4 5d 1.15 N/A 1.17  5d′ 1.14 N/A 1.14 9/228.6 5 5e 1.47 N/A1.49  5e′ 1.16 N/A 1.16 8/203.2 6 5f 1.02 N/A 1.02  5f′ 0.98 N/A 0.988/203.2 7 5g 1.06 N/A 1.07  5g′ 0.94 N/A 0.96 8/203.2 8 5h 0.92 N/A 0.93 5h′ 1.12 N/A 1.14  8/203.2** Output Water Temperature 82 C. *Distancefrom water inlet to center of first electrode set **Distance from centerof last electrode set to water outlet

Atomic Absorption Spectroscopy (AAS) samples were prepared andmeasurement values were obtained, as discussed in Example 6. Table 12ishows the results. Note that Table 12i includes a column entitled“Electrode Configuration”. This column contains characters of “1” and“0” and “X”. The “1's” represent an electrode configurationcorresponding to Electrode Set #1 (i.e., a 1, 5 combination). The “0's”represent an electrode combination of 5, 5′. The character “X”represents that no electrodes were present. Thus, for example, “AT084”is represented by “1000XXXX” which means a four electrode setcombination was used to make “AT084” and the combination corresponded toSet #1=1, 5; Set #2=5, 5; Set #3=5, 5 and Set #4=5, 5 (there were noSets after Set #4, as represented by “XXXX”).

TABLE 12i Measured Measured Average Particle Electrode Ag PPM Ag PPMSize Diameter Run ID Configuration (initial) (10 days) Range (Initial)AT097 1XXXXXXX 6.5 6.5 2 nm AT086 10XXXXXX 14.9 13.4 3-7 nm AT085100XXXXX 19.2 18.4 3-8 nm AT084 1000XXXX 24.1 22.9 4-8 nm AT083 10000XXX30.4 28.1 6-15 nm AT082 100000XX 34.2 27.4 20-100 nm AT081 1000000X 36.729.3 40-120 nm AT080 10000000 40.9 31.6 40-150 nm

Table 12i includes a column entitled “Measured Ag PPM (initial)”. Thiscolumn corresponds to the silver content of each of the eight solutionsmeasured within one hour of its production. As shown, the measured ppmincreases with each added Electrode Set, wherein the Run AT080 producesa ppm level for silver comparable in amount to Run ID AT031 of Example3. However, another column entitled, “Measured Ag PPM (10 days)” showsdata which tells another story. Specifically, the “initial” and “10 day”PPM measurements are essentially the same (e.g., within operation errorof the AAS) for samples corresponding to Run Id's AT097, AT086, AT085,AT084 and AT083. This means that essentially no significant settling ofthe constituent particles found in five of the eight runs occurred.However, once samples associated with Run ID AT082, AT081 and AT080 wereexamined after 10 days, a significant portion of the constituentparticles had settled, with samples taken from Run AT080 losing about 10ppm out of 40 ppm due to particulate settling.

In order to obtain an idea of what particle sizes were being produced ineach of the eight samples associated with this Example 7, a dynamiclight scattering (DLS) approach was utilized. Specifically, dynamiclight scattering methods utilizing variations of scattered lightintensities from an LED laser were measured over time to determine anychanges in intensity from particle motion due to Brownian Motion. Theinstrument used to perform these measurements was a VISCOTEK 802 DLSwith Dual Alternating Technology (D.A.T.).

All measurements were made using a 12 μL quartz cell, which was placedinto a temperature controlled cell block. One 827.4 nm laser beam waspassed through the solution to be measured. Scattering intensities weremeasured using a CCD detector with an optical view path mountedtransversely to that of the laser. Experimental data was thenmathematically transformed using variation of Einstein-Stokes andRayleigh equations to derive values representative of particle size anddistribution information. Data collection and math transforms wereperformed using Viscotek Omnisize version 3,0,0,291 software. Thisinstrument hardware and software reliably provides measurements forparticles with a radius from 0.8 nm to 2 μm.

This technique works best when the solution is free of micro-bubbles andparticles subject to Stokes settling motion (some of which was clearlyoccurring in at least three of the samples in this Example 7). Allvessels used to contain and prepare materials to be tested were rinsedand blow-dried to remove any debris. All water used to prepare vesselsand samples was doubly de-ionized and 0.2 μm filtered. If solvent isneeded, use only spectrographic grade isopropyl alcohol. All were rinsedwith clean water after solvent exposure, and wiped only with cleanlint-free cotton cloth.

An aliquot of solution sample, about 3 ml in total volume, was drawninto a small syringe and then dispensed into a clean about 4 dram glasssample vial. Two (2) syringe filters (0.45 μm) were fixed onto thesyringe during this operation to doubly filter the sample, thus removingany large particles not intended as part of the solution. This samplewas placed into a small vacuum chamber, where it was subjected to a 1minute exposure to a low-level vacuum (<29.5 inches Hg) to boil thesuspension, removing suspended micro-bubbles. The vacuum was drawnthrough a small dual-stage rotary vacuum pump such as a Varian SD-40.Using a glass Tuberculin syringe with a 20 gauge or smaller bluntedneedle, sample was withdrawn to fill the syringe and then rinsed, thenplaced into the 12 μL sample cell/cuvette. Additional like-type syringeswere used to withdraw used sample and rinse fluids from this cell. Thefilled cuvette was inspected for obvious entrapped bubbles within theoptical path.

This cell was inserted into the holder located in the VISCOTEK 802 DLS.Prior to this step, the instrument was allowed to fully warm tooperating temperature for about 30 minutes and operating “OmniSIZE”software loaded in the controlling computer. This software willcommunicate and set-up the instrument to manufacturer prescribedconditions. Select a “new” measurement. Validate that the correct samplemeasurement parameters are selected, i.e.; temperature of 40° C.,“Target” laser attenuation value of 300k counts per second, 3 secondmeasurement duration, water as the solvent, spike and drift respectivelyat 20% and 15%. Correct if needed. Then select “Tools-Options” from thecontrolling menu bar. Insure proper options are annotated; i.e.resolution at 200, ignore first 2 data points, peak reporting thresholdof 0 and 256 correlator channels.

Once the sample was placed into the holder, the cover lid was securelyclosed causing the laser shutter to open. The sample was allowed totemperature stabilize for 5 to 10 minutes. On the menu tools bar,“Auto-Attenuate” was selected to cause the adjustment of laser power tofit the measurement requirements. Once the instrument and sample wasset-up, the scatter intensity graphic display was observed. Patternsshould appear uniform with minimal random spikes due to entrainednano/micro-bubbles or settling large particles.

A measurement was then performed. The developing correlation curve wasalso observed. This curve should display a shape as an “inverted S” andnot “spike” out-of-limits. If the set-up was correct, parameters wereadjusted to collect 100 measurements and “run” was then selected. Theinstrument auto-collected data and discarded correlation curves, notexhibiting Brownian motion behavior. At measurement series completion,retained correlation curves were inspected. All should exhibit expectedshape and displayed between 30% and 90% expected motion behaviors. Atthis point, collected data was saved and software calculated particlesize information. The measurement was repeated to demonstratereproducibility. Resultant graphic displays were then inspected.Residuals should appear randomly dispersed and data measurement pointmust follow calculated theoretical correlation curve. The graphicdistribution display was limited to 0.8 nm to 2 μm. The IntensityDistribution and Mass Distribution histograms were reviewed to findparticle sizes and relative proportions of each, present in thesuspension. All information was then recorded and documented.

FIG. 57A corresponds to a representative Viscotek output for AT097; andFIG. 57B corresponds to a representative Viscotek output for AT080. Thenumbers reported in FIGS. 57A and 57B correspond to the radii ofparticles detected in each solution. It should be noted that multiple(e.g., hundreds) of data-points were examined to give the numbersreported in Table 12i, and FIGS. 57A and 57B are just a selection fromthose measured values.

In an effort to understand further the particles produced as a functionof the different electrode combinations set forth in the Example 7, SEMphotomicrographs of similar magnification were taken of each driedsolution corresponding to each of the eight solutions made in thisExample. These SEM photomicrographs are shown in FIGS. 58A-58G. FIG. 58Acorresponds to a sample from Run ID AT086 and FIG. 58G corresponds to asample from Run ID AT080. Each SEM photomicrograph shows a “1μ” (i.e., 1micron) bar. The general observable trend from these photomicrographs isthat particle sizes gradually increase from samples AT086 through AT083,but thereafter start to increase rapidly within samples fromAT082-AT080. It should be noted that the particulate matter was so smalland of such low concentration that no images are available for Run IDAT097.

It should be noted that samples were prepared for the SEM by allowing asmall amount of each solution produced to air dry on a glass slide.Accordingly, it is possible that some crystal growth may have occurredduring drying. However, the amount of “growth” shown in each of samplesAT082-AT080 is more than could possibly have occurred during dryingalone. It is clear from the SEM photomicrographs that cubic-shapedcrystals are evident in AT082, AT081 and AT080. In fact, nearly perfectcubic-shaped crystals are shown in FIG. 58G, associated with sampleAT080.

Accordingly, without wishing to be bound by any particular theory orexplanation, when comparing the results of Example 7 with Example 6, itbecomes clear that the creation of the plasma 4 has a profound impact onthis inventive process. Moreover, once the plasma 4 is established,conditions favor the production of metallic-based constituents,including silver-based nanoparticles, including the apparent growth ofparticles as a function of each new electrode set 5, 5′ providedsequentially along the trough member 30. However, if the goal of theprocess is to maintain the suspension of metallic-based nanoparticles insolution, then, under the process conditions of this Example 7, some ofthe particles produced begin to settle out near the last three ElectrodeSets (i.e., Run Id's AT082, AT081 and AT080). However, if the goal ofthe process is to achieve particulate matter settling, then that goalcan be achieved by following the configurations in Runs AT082, AT081 andAT080.

UV-Vis spectra were obtained for each of the settled mixturesAT097-AT080. Specifically, UV-Vis spectra were obtained as discussedabove herein (see the discussion in the section entitled,“Characterization of Materials of Examples 1-5 and Mixtures Thereof”).FIG. 59A shows the UV-Vis Spectra for each of samples AT097-AT080 forthe wavelengths between 200 nm-220 nm. The spectra corresponding toAT097 is off the chart for this scale, so the expanded view in FIG. 59Bhas been provided. It is interesting to note that for each set ofelectrodes 5, 5′ that are sequentially added along the trough member 30,the height or amplitude of the peak occurring around 200 nm associatedwith AT097 diminishes in amount.

UV-Vis spectra for these same eight samples are also shown in FIG. 59C.Specifically, this FIG. 59C examines wavelengths in the 220 nm-620 nmrange. Interestingly, the three samples corresponding to AT080, AT081and AT082, are all significantly above the other five spectra.

In an effort to determine efficacy against an E. coli bacteria(discussed in greater detail earlier herein), each of the eightsolutions made according to this Example 7 were all diluted to the exactsame ppm for silver in order to compare their relative efficacies in anormalized approach. In this regard, the normalization procedure was,for each of the samples, based on the ppm measurements taken after tendays of settling. Accordingly, for example, samples made according toRun AT080 were diluted from 31.6 ppm down to 4 ppm; whereas the samplesassociated with Run AT083 were diluted from 28.1 ppm, down to 4 ppm.These samples were then further diluted to permit Bioscreen measurementsto be performed, as discussed above herein.

FIG. 60 corresponds to a Bioscreen C Microbiology Reader Run that wasperformed with the same ppm's of silver taken from each of samplesAT097-AT080. The results in FIG. 60 are striking in that the efficacy ofeach of the eight solutions line up perfectly in sequence with thehighest efficacy being AT086 and the lowest efficacy being AT080. Itshould be noted that efficacy for sample AT097 was inadvertently notincluded in this particular Bioscreen run. Further, while results withinany Bioscreen run are very reliable for comparison purposes, resultsbetween Bioscreen runs performed at separate times may not providereliable comparisons due to, for example, the initial bacteriaconcentrations being slightly different, the growth stage of thebacteria being slightly different, etc. Accordingly, no comparisons havebeen made in any of the Examples herein between Bioscreen runs performedat different times.

Example 8 Manufacturing Silver-Based Nanoparticles/NanoparticleSolutions AT089, AT090 and AT091 Using One or Two Plasmas

This Example utilizes the same basic apparatus used to make thesolutions of Examples 1-5, however, this Example uses only a singleplasma 4 to make AT090 (i.e., similar to AT080); two plasmas 4 to makeAT091 (i.e., similar to AT031); and two plasmas 4 to make AT089 (firsttime run), wherein Electrode Set #1 and Electrode Set #8 both utilizeplasmas 4. This Example also utilizes 99.95% pure silver electrodes foreach of electrodes 1 and 5 in each Electrode Set.

Tables 13a, 13b and 13c summarize portions of electrode design,configuration, location and operating voltages. As shown in Tables13a-13c, the target voltages were on average highest associated withAT089 and lowest associated with AT091.

Further, bar charts of the actual and target voltages for each electrodein each electrode set, are shown in FIGS. 61A, 61B and 61C. Accordingly,the data contained in Tables 13a-13c, as well as FIGS. 61A, 61B and 61C,give a complete understanding of the electrode design in each electrodeset as well as the target and actual voltages applied to each electrodefor the manufacturing processes.

TABLE 13a Run ID: AT090 Flow Rate: 200 ml/min Target Distance DistanceAverage Voltage “c-c” “x” Voltage Set # Electrode # (kV) in/mm in/mm(kV)  7/177.8* 1 1a 2.03 0.22/5.59 2.09 5a 1.62 N/A 1.69 8/203.2 2 5b0.87 N/A 0.94  5b′ 1.08 N/A 1.11 8/203.2 3 5c 1.04 N/A 1.10  5c′ 0.94N/A 0.97 8/203.2 4 5d 1.23 N/A 1.26  5d′ 1.24 N/A 1.30 9/228.6 5 5e 1.42N/A 1.47  5e′ 1.11 N/A 1.12 8/203.2 6 5f 1.03 N/A 1.01  5f′ 1.01 N/A1.03 8/203.2 7 5g 1.15 N/A 1.13  5g′ 0.94 N/A 1.02 8/203.2 8 5h 0.81 N/A1.04  5h′ 1.03 N/A 1.04  8/203.2** Output Water Temperature 85 C.*Distance from water inlet to center of first electrode set **Distancefrom center of last electrode set to water outlet

TABLE 13b Run ID: AT091 Flow Rate: 200 ml/min Target Distance DistanceAverage Voltage “c-c” “x” Voltage Set # Electrode # (kV) in/mm in/mm(kV)  7/177.8* 1 1a 2.04 0.22/5.59 2.04 5a 1.67 N/A 1.66 8/203.2 2 5b0.94 N/A 0.93  5b′ 1.11 N/A 1.10 8/203.2 3 5c 1.01 N/A 0.98  5c′ 1.07N/A 1.05 8/203.2 4 1d 1.44 0.19/4.83 1.41 5d 1.12 N/A 1.11 9/228.6 5 5e1.09 N/A 1.07  5e′ 0.56 N/A 0.55 8/203.2 6 5f 0.72 N/A 0.71  5f′ 0.72N/A 0.70 8/203.2 7 5g 0.79 N/A 0.81  5g′ 0.73 N/A 0.68 8/203.2 8 5h 0.64N/A 0.68  5h′ 0.92 N/A 0.89  8/203.2** Output Water Temperature 73 C.*Distance from water inlet to center of first electrode set **Distancefrom center of last electrode set to water outlet

TABLE 13c Run ID: AT089 Flow Rate: 200 ml/min Target Distance DistanceAverage Voltage “c-c” “x” Voltage Set # Electrode # (kV) in/mm in/mm(kV)  7/177.8* 1 1a 2.18 0.22/5.59 2.16 5a 1.80 N/A 1.77 8/203.2 2 5b0.99 N/A 0.99  5b′ 1.15 N/A 1.13 8/203.2 3 5c 1.12 N/A 1.14  5c′ 1.00N/A 0.98 8/203.2 4 5d 1.33 N/A 1.27  5d′ 1.35 N/A 1.32 9/228.6 5 5e 1.51N/A 1.49  5e′ 1.16 N/A 1.12 8/203.2 6 5f 1.05 N/A 1.00  5f′ 1.04 N/A1.01 8/203.2 7 5g 1.15 N/A 1.11  5g′ 1.14 N/A 1.10 8/203.2 8 1h 1.230.19/4.83 1.19 5h 1.31 N/A 1.27  8/203.2** Output Water Temperature 78C. *Distance from water inlet to center of first electrode set**Distance from center of last electrode set to water outlet

Atomic Absorption Spectroscopy (AAS) samples were prepared andmeasurement values were obtained, as discussed in Example 6. Table 13dshows the results. Note that Table 13d includes a column entitled“Electrode Configuration”. This column contains characters of “1” and“0”. The “l's” represent an electrode configuration corresponding toElectrode Set #1 (i.e., a 1, 5 combination). The “0's” represent anelectrode combination of 5, 5′. Thus, for example, “AT089” isrepresented by “10000001” which means an eight electrode set combinationwas used to make “AT089” and the combination corresponded to Set #1=1,5; Sets #2-#7=5, 5; and Set #8=1, 5.

TABLE 13d Measured Measured Electrode Ag PPM Ag PPM Run ID Configuration(initial) (20 hours) AT089 10000001 44.3 45.0 AT090 10000000 40.8 37.2AT091 10010000 43.6 44.3

Table 13d includes a column entitled “Measured Ag PPM (initial)”. Thiscolumn corresponds to the silver content of each of the eight solutionsmeasured within one hour of its production. As shown, the measured ppmfor each of the three Runs were generally similar. However, anothercolumn entitled, “Measured Ag PPM (20 hours)” shows that the “initial”and “20 hours” PPM measurements are essentially the same (e.g., withinoperation error of the AAS) for samples corresponding to Run Id's AT089and AT091. This means that essentially no significant settling of theconstituent particles found in these runs occurred. However, the sampleassociated with Run ID AT090 was examined after 20 hours, a significantportion of the constituent particles had settled, with the samples takenfrom Run AT089 losing about 3.6 ppm out of 40 ppm due to particulatesettling.

As discussed in Example 7, a dynamic light scattering (DLS) approach wasutilized to obtain average particle size made in each of these threesamples. The largest particles were made in AT090; and the smallestparticles were made in AT091. Specifically, FIG. 62A corresponds toAT090; FIG. 62B corresponds to AT091; and FIG. 62C corresponds to AT089.

In an effort to determine efficacy against an E. coli bacteria(discussed in greater detail earlier herein), each of the threesolutions made according to this Example 8 were all diluted to the exactsame ppm for silver in order to compare their relative efficacies in anormalized manner. In this regard, the normalization procedure was, foreach of the samples, based on the ppm measurement taken after twentyhours of settling. Accordingly, for example, samples made according toRun AT090 were diluted from 37.2 ppm down to 4 ppm; whereas the samplesassociated with Run AT091 were diluted from 44.0 ppm, down to 4 ppm.These samples were then further diluted to permit Bioscreen measurementsto be performed, as discussed above herein. FIG. 63 corresponds to aBioscreen C Microbiology Reader Run that was performed with the sameppm's of silver taken from each of samples AT089-AT091. The results inFIG. 63 show that the efficacy of each of the three solutions line upcorresponding to the particle sizes shown in FIGS. 62A-62C, with thehighest efficacy being AT091 and the lowest efficacy being AT090.Further, while results within any Bioscreen run are very reliable forcomparison purposes, results between Bioscreen runs performed atseparate times may not provide reliable comparisons due to, for example,the initial bacteria concentrations being slightly different, the growthstage of the bacteria being slightly different, etc. Accordingly, nocomparisons have been made herein between Bioscreen runs performed atdifferent times.

Example 9 Manufacturing Silver-Based Nanoparticles/NanoparticleSolutions AT091, AT092, AT093, AT094 and AT095 Using Plasmas in MultipleAtmospheres

This Example utilizes essentially the same basic apparatus used to makethe solutions of Examples 1-5, however, this Example uses two plasmas 4occurring in a controlled atmosphere environment. Controlled atmosphereswere obtained by using the embodiment shown in FIG. 28H. Specifically,for Electrode Set #1 and Electrode Set #4, this Example uses a “1, 5”electrode configuration wherein the electrode 1 creates a plasma in eachof the following atmospheres: air, nitrogen, reducing, ozone and helium.All other Electrode Sets #2, #3 and #5-#8, have a “5, 5′” electrodeconfiguration. This Example also utilizes 99.95% pure silver electrodesfor each of electrodes 1 and 5 in each Electrode Set.

Tables 14a-14e summarize portions of electrode design, configuration,location and operating voltages. As shown in Tables 14a-14e, the targetvoltages were set to a low of about 400-500 volts (reducing atmosphereand ozone) and a high of about 3,000 volts (helium atmosphere).

Further, bar charts of the actual and target voltages for each electrodein each electrode set, are shown in FIGS. 64A-64E. Accordingly, the datacontained in Tables 14a-14e, as well as FIGS. 64A-64E, give a completeunderstanding of the electrode design in each electrode set as well asthe target and actual voltages applied to each electrode for themanufacturing processes. The atmospheres used for each plasma 4 for eachelectrode 1 for Electrode Set #1 and Electrode Set #4 were as follows:AT091—Air; AT092—Nitrogen; AT093—Reducing or Air-Deprived; AT094—Ozone;and AT095—Helium. The atmospheres for each of Runs AT092-AT095 wereachieved by utilizing the atmosphere control device 35 shown, forexample, in FIG. 28H. Specifically, a nitrogen atmosphere was achievedaround each electrode 1, 5 in Electrode Set #1 and Electrode Set #4 byflowing nitrogen gas (high purity) through tubing 286 into the inletportion 37 of the atmosphere control device 35 shown in FIG. 28H. Theflow rate of nitrogen gas was sufficient so as to achieve positivepressure of nitrogen gas by causing the nitrogen gas to create apositive pressure on the water 3 within the atmosphere control device35.

Likewise, the atmosphere of ozone (AT094) was achieved by creating apositive pressure of ozone created by an ozone generator and inputtedinto the atmosphere control device 35, as discussed above herein. Itshould be noted that significant nitrogen content was probably presentin the supplied ozone.

Further, the atmosphere of helium (AT095) was achieved by creating apositive pressure of helium inputted into the atmosphere control device35, as discussed above herein.

The atmosphere of air was achieved without using the atmosphere controldevice 35.

The reducing atmosphere (or air-deprived atmosphere) was achieved byproviding the atmosphere control device 35 around each electrode 1, 5 inElectrode Sets #1 and #4 and not providing any gas into the inletportion 37 of the atmosphere control devices 35. In this instance, theexternal atmosphere (i.e., an air atmosphere) was found to enter intothe atmosphere control device 35 through the hole 37 and the plasma 4created was notably much more orange in color relative to the airatmosphere plasma.

In an effort to understand the composition of each of the plasmas 4, a“Photon Control Silicon CCD Spectrometer, SPM-002-E” (from Blue HillOptical Technologies, Westwood, Mass.) was used to collect the emissionspectra for each of the plasmas 4.

Specifically, in reference to FIGS. 65A and 65B, the Photon ControlSilicon CCD Spectrometer 500, was used to collect spectra (200-1090 nm,0.8/2.0 nm center/edge resolution) on each plasma 4 generated betweenthe electrode 1 and the surface 2 of the water 3. The Spectrometer 500was linked via a USB cable to a computer (not shown) loaded with PhotonControl Spectrometer software, revision 2.2.3. A 200 μm core opticalfiber patch cable 502 (SMA-905, Blue Hill Optical Technologies) wasmounted on the end of a Plexiglas support 503. A laser pointer 501(Radio Shack Ultra Slim Laser Pointer, #63-1063) was mounted on theopposite side 506 of the plexiglas support. This assembly 503 wascreated so that the optical cable 502 could be accurately and repeatedlypositioned so that it was directly aimed toward the same middle portionof each plasma 4 formed by using the laser pointer 501 as an aimingdevice.

Prior to the collection of any spectra created by each plasma 4, theatmosphere control device 35 was saturated with each gas for 30 secondsand a background spectrum was collected with 2 second exposure set inthe software package. The plasma 4 was active for 10 minutes prior toany data collection. The primary spot from the laser 501 was alignedwith the same point each time. Three separate spectra were collected foreach run and then averaged. The results of each spectra are shown inFIGS. 66A-66E (discussed later herein in this Example).

TABLE 14a Run ID: AT091 Flow Rate: 200 ml/min Atmosphere For Set #1 andSet #4: Air Target Distance Distance Average Voltage “c-c” “x” VoltageSet # Electrode # (kV) in/mm in/mm (kV)  7/177.8* 1 1a 2.04 0.22/5.592.04 5a 1.67 N/A 1.66 8/203.2 2 5b 0.94 N/A 0.93  5b′ 1.11 N/A 1.108/203.2 3 5c 1.01 N/A 0.98  5c′ 1.07 N/A 1.05 8/203.2 4 1d 1.440.19/4.83 1.41 5d 1.12 N/A 1.11 9/228.6 5 5e 1.09 N/A 1.07  5e′ 0.56 N/A0.55 8/203.2 6 5f 0.72 N/A 0.71  5f′ 0.72 N/A 0.70 8/203.2 7 5g 0.79 N/A0.81  5g′ 0.73 N/A 0.68 8/203.2 8 5h 0.64 N/A 0.68  5h′ 0.92 N/A 0.89 8/203.2** Output Water Temperature 73 C. *Distance from water inlet tocenter of first electrode set **Distance from center of last electrodeset to water outlet

TABLE 14b Run ID: AT092 Flow Rate: 200 ml/min Atmosphere For Set #1 andSet #4: Nitrogen Target Distance Distance Average Voltage “c-c” “x”Voltage Set # Electrode # (kV) in/mm in/mm (kV)  7/177.8* 1 1a 2.390.22/5.59 2.27 5a 2.02 N/A 1.99 8/203.2 2 5b 1.39 N/A 1.30  5b′ 1.51 N/A1.54 8/203.2 3 5c 1.49 N/A 1.47  5c′ 1.50 N/A 1.52 8/203.2 4 1d 1.640.19/4.83 1.66 5d 1.33 N/A 1.31 9/228.6 5 5e 1.46 N/A 1.47  5e′ 1.05 N/A0.98 8/203.2 6 5f 1.18 N/A 1.13  5f′ 1.13 N/A 1.11 8/203.2 7 5g 1.26 N/A1.20  5g′ 1.17 N/A 1.03 8/203.2 8 5h 0.94 N/A 0.87  5h′ 1.12 N/A 1.07 8/203.2** Output Water Temperature 88 C. *Distance from water inlet tocenter of first electrode set **Distance from center of last electrodeset to water outlet

TABLE 14c Run ID: AT093 Flow Rate: 200 ml/min Atmosphere For Set #1 andSet #4: Reducing or Air-Deprived Target Distance Distance AverageVoltage “c-c” “x” Voltage Set # Electrode # (kV) in/mm in/mm (kV) 7/177.8* 1 1a 2.04 0.22/5.59 2.02 5a 1.50 N/A 1.49 8/203.2 2 5b 0.76N/A 0.76  5b′ 1.02 N/A 1.03 8/203.2 3 5c 0.91 N/A 0.91  5c′ 0.98 N/A0.99 8/203.2 4 1d 1.38 0.19/4.83 1.39 5d 1.01 N/A 0.99 9/228.6 5 5e 0.94N/A 0.92  5e′ 0.39 N/A 0.38 8/203.2 6 5f 0.60 N/A 0.58  5f′ 0.50 N/A0.48 8/203.2 7 5g 0.68 N/A 0.65  5g′ 0.55 N/A 0.56 8/203.2 8 5h 0.59 N/A0.59  5h′ 0.89 N/A 0.87  8/203.2** Output Water Temperature 75 C.*Distance from water inlet to center of first electrode set **Distancefrom center of last electrode set to water outlet

TABLE 14d Run ID: AT094 Flow Rate: 200 ml/min Atmosphere For Set #1 andSet #4: Ozone Target Distance Distance Average Voltage “c-c” “x” VoltageSet # Electrode # (kV) in/mm in/mm (kV)  7/177.8* 1 1a 2.24 0.22/5.592.20 5a 1.73 N/A 1.74 8/203.2 2 5b 0.93 N/A 0.95  5b′ 1.16 N/A 1.188/203.2 3 5c 1.09 N/A 1.10  5c′ 1.15 N/A 1.17 8/203.2 4 1d 1.450.19/4.83 1.47 5d 1.08 N/A 1.10 9/228.6 5 5e 0.99 N/A 1.00  5e′ 0.43 N/A0.45 8/203.2 6 5f 0.64 N/A 0.63  5f′ 0.52 N/A 0.56 8/203.2 7 5g 0.71 N/A0.74  5g′ 0.63 N/A 0.64 8/203.2 8 5h 0.66 N/A 0.67  5h′ 0.95 N/A 0.95 8/203.2** Output Water Temperature 76 C. *Distance from water inlet tocenter of first electrode set **Distance from center of last electrodeset to water outlet

TABLE 14e Run ID: AT095 Flow Rate: 200 ml/min Atmosphere For Set #1 andSet #4: Helium Target Distance Distance Average Voltage “c-c” “x”Voltage Set # Electrode # (kV) in/mm in/mm (kV)  7/177.8* 1 1a 3.090.22/5.59 3.11 5a 2.98 N/A 2.96 8/203.2 2 5b 2.81 N/A 2.80  5b′ 2.86 N/A2.83 8/203.2 3 5c 2.38 N/A 2.38  5c′ 2.32 N/A 2.30 8/203.2 4 1d 2.640.19/4.83 2.58 5d 2.50 N/A 2.49 9/228.6 5 5e 2.06 N/A 2.07  5e′ 1.64 N/A1.63 8/203.2 6 5f 1.34 N/A 1.36  5f′ 1.31 N/A 1.31 8/203.2 7 5g 1.27 N/A1.28  5g′ 1.12 N/A 1.12 8/203.2 8 5h 1.08 N/A 1.08  5h′ 1.26 N/A 1.25 8/203.2** Output Water Temperature 95 C. *Distance from water inlet tocenter of first electrode set **Distance from center of last electrodeset to water outlet

Atomic Absorption Spectroscopy (AAS) samples were prepared andmeasurement values were obtained, as discussed in Example 6. Table 14fshows the results. Note that Table 14f includes a column entitled“Electrode Configuration”. This column contains characters “1” and “0”.The “1's” represent an electrode configuration corresponding toElectrode Set #1 (i.e., a 1, 5 combination). The “0's” represent anelectrode combination of 5, 5′. Thus, for example, “AT091” isrepresented by “10010000” which means an eight electrode set combinationwas used to make “AT091” and the combination corresponded to Set #1=1,5; Set #2=5, 5; Set #3=5, 5; Set #4=1, 5 and Set #5-Set #8=5, 5.

TABLE 14f Electrode Measured Run ID Configuration Ag PPM AtmosphereAT091 10010000 44.0 Air AT092 10010000 40.3 Nitrogen AT093 10010000 46.8Reducing AT094 10010000 44.5 Ozone AT095 10010000 28.3 Helium

Table 14f includes a column entitled “Measured Ag PPM”. This columncorresponds to the silver content of each of the eight solutions. Asshown, the measured ppm produced in each of the atmospheres of air,nitrogen, reducing and ozone were substantially similar. However, theatmosphere of helium (i.e., AT095) produced a much lower ppm level.Also, the size of particulate matter in the AT095 solution wassignificantly larger than the size of the particulate matter in each ofthe other four solutions. The particulate sizes were determined bydynamic light scattering methods, as discussed above herein.

It is clear from FIGS. 66A-66E that each spectra shown therein createdfrom the plasma 4 had a number of very prominent peaks. For example,those prominent peaks associated with each of the atmospheres of air,nitrogen, reducing and ozone all have strong similarities. However, thespectral peaks associated with the spectra creating by the plasma 4(i.e., when helium was provided as the atmosphere) are quite differentfrom the other four peaks. In this regard, FIG. 66A shows the completespectral response for each plasma 4 for each of the gasses used in thisExample over the entire wavelength range of 200-1000 nm. FIGS. 66B and66C focus on certain portions of the spectra of interest and identify byname the atmospheres associated with each spectrum. FIGS. 66D and 66Eidentify specific common peaks in each of these spectra. Specifically,FIGS. 67A-67F are excerpted from the articles discussed above herein.Those FIGS. 67A-67F assist in identifying the active peaks in the plasma4 of this Example 9. It is clear that spectral peaks associated with thehelium atmosphere are quite different from spectral peaks associatedwith the other four atmospheres.

In an effort to determine efficacy against an E. coli bacteria(discussed in greater detail earlier herein), each of the five solutionsmade according to this Example 9 were all diluted to the exact same ppmfor silver in order to compare their relative efficacies in a normalizedmanner. Accordingly, for example, samples made according to Run AT091were diluted from 44.0 ppm down to 4 ppm; whereas the samples associatedwith Run AT095 were diluted from 28.3 ppm, down to 4 ppm. These sampleswere then further diluted to permit Bioscreen measurements to beperformed, as discussed above herein. FIG. 68 corresponds to a BioscreenC Microbiology Reader Run that was performed with the same ppm's ofsilver taken from each of samples AT091-AT095. The results in FIG. 68show the highest efficacy being AT094 and AT096 (note: AT096 was madeaccording to Example 10, and shall be discussed in greater detailtherein) and the lowest efficacy being AT095. Further, while resultswithin any Bioscreen run are very reliable for comparison purposes,results between Bioscreen runs performed at separate times may notprovide reliable comparisons due to, for example, the initial bacteriaconcentrations being slightly different, the growth stage of thebacteria being slightly different, etc. Accordingly, no comparisons havebeen made herein between Bioscreen runs performed at different times.

Example 10 Manufacturing Silver-Based Nanoparticles/NanoparticleSolution AT096, Using a Diode Bridge to Rectify an AC Power Source toForm Plasmas

This Example utilizes essentially the same basic apparatus used to makethe solutions of Examples 1-5, however, this Example uses two plasmas 4formed by a DC-like Power Source (i.e., a diode bridge-rectified powersource). Specifically, for Electrode Set #1 and Electrode Set #4, thisExample uses a “1, 5” electrode configuration wherein the electrode 1creates a plasma 4 in accordance with the power source shown in FIG.32C. All other Electrode Sets #2, #3 and #5-#8, had a “5, 5′” electrodeconfiguration. This Example also utilizes 99.95% pure silver electrodesfor each of electrodes 1 and 5 in each Electrode Set.

Table 15 summarizes portions of electrode design, configuration,location and operating voltages. As shown in Table 15, the targetvoltages were set to a low of about 400 volts (Electrode Set #4) and ahigh of about 1,300 volts (Electrode Set #3).

Further, bar charts of the actual and target voltages for each electrodein each electrode set, are shown in FIG. 69. Accordingly, the datacontained in Table 15, as well as FIG. 69, give a complete understandingof the electrode design in each electrode set as well as the target andactual voltages applied to each electrode for the manufacturingprocesses.

TABLE 15 Run ID: AT096 Flow Rate: 200 ml/min Target Distance DistanceAverage Voltage “c-c” “x” Voltage Set # Electrode # (kV) in/mm in/mm(kV)  7/177.8* 1 1a 0.76 0.19/4.83 0.69 5a 0.68 N/A 0.68 8/203.2 2 5b1.25 N/A 1.22  5b′ 1.13 N/A 1.11 8/203.2 3 5c 1.18 N/A 1.15  5c′ 1.28N/A 1.27 8/203.2 4 1d 0.41 0.19/4.83 0.47 5d 0.64 N/A 0.63 9/228.6 5 5e1.02 N/A 0.99  5e′ 0.93 N/A 0.91 8/203.2 6 5f 0.76 N/A 0.74  5f′ 0.76N/A 0.76 8/203.2 7 5g 0.91 N/A 0.90  5g′ 0.80 N/A 0.79 8/203.2 8 5h 0.75N/A 0.74  5h′ 0.93 N/A 0.93  8/203.2** Output Water Temperature 80 C.*Distance from water inlet to center of first electrode set **Distancefrom center of last electrode set to water outlet

Atomic Absorption Spectroscopy (AAS) samples were prepared andmeasurement values were obtained, as discussed in Example 6. Table 15ashows the results. Note that Table 15a includes a column entitled“Electrode Configuration”. This column contains characters “1*” and “0”.The “1*” represents an electrode configuration corresponding toElectrode Set #1 (i.e., a 1, 5 combination, wherein the electrode 1 isnegatively biased and the electrode 5 is positively biased. The “0's”represent an electrode combination of 5, 5′.

TABLE 15a Electrode Measured Run ID Configuration Ag PPM AtmosphereAT096 1*001*0000 51.2 Air

Table 15a includes a column entitled “Measured Ag PPM”. This columncorresponds to the silver content of the solution. As shown, themeasured ppm was 51.2 ppm, which was substantially higher than any othersamples made by the other eight electrode sets utilized in any otherExample.

In an effort to determine efficacy against an E. coli bacteria(discussed in greater detail earlier herein), this solution AT096 wastested against each of the five solutions made according to Example 9above herein. Specifically, all of the five solutions from Example 9 andAT096 were diluted to the exact same ppm for silver in order to comparetheir relative efficacies in a normalized manner as discussed in Example9. FIG. 68 corresponds to a Bioscreen C Microbiology Reader Run that wasperformed with the same ppm's of silver taken from each of samplesAT092-AT096. The results in FIG. 68 show that AT096 was among the bestperforming solutions. Further, while results within any Bioscreen runare very reliable for comparison purposes, results between Bioscreenruns performed at separate times may not provide reliable comparisonsdue to, for example, the initial bacteria concentrations being slightlydifferent, the growth stage of the bacteria being slightly different,etc. Accordingly, no comparisons have been made herein between Bioscreenruns performed at different times.

The atmosphere used for AT096 was air, and the corresponding spectra ofthe air plasma is shown in FIGS. 70A, 70B and 70C. These spectra aresimilar to those set forth in FIGS. 66A, 66B and 66C. Additionally,FIGS. 70A, 70B and 70C show spectra associated with the atmospheres ofnitrogen, reducing or air-deprived and helium, all produced according tothe set-up conforming to that used to make the plasma 4 in AT096. Theseatmospheres and the measurements associated therewith, were made inaccordance with the teachings in Example 9.

Similarly, FIGS. 71A, 71B and 71C show a similar set of spectra takenfrom plasmas 4 when the polarity of the electrode 1 used earlier in thisExample has been reversed. In this regard, all of the atmospheres forair, nitrogen, reducing or air-deprived, ozone and helium are alsoutilized but in this case the electrode 1 has become positively biasedand the electrode 5 (i.e., the surface 2 of the water 3) has becomenegatively biased.

Example 11 Efficacy and Cytotoxicity Testing of Related NanoparticleSolutions

This Example follows the teachings of Examples 2 [AT060], 3[AT031-AT064] and 4 [BT006-BT012] to manufacture two differentsilver-based nanoparticle/nanoparticle solutions and one zinc-basednanoparticle/nanoparticle solution. Additionally, a new and differentsolution (i.e., PT001) based in part on the inventive process for makingBT006 and BT012 was also produced. Once produced, three solutions weretested for efficacy and cytotoxicity.

Specifically, the solution made by the method of Example 2 (i.e., AT060)was tested for cytotoxicity against Murine Liver Epithelial Cells, asdiscussed above herein. The results are shown in FIG. 72A. Likewise, asolution produced according to Example 3 (i.e., AT031) was made “AT064”and was also likewise tested for cytotoxicity. The results are shown inFIG. 72B. Further, material produced according to Example 4 (i.e.,BT006) was made and designated “BT012” and was likewise tested forcytotoxicity. The results are shown in FIG. 72C.

Mixtures of the materials (i.e., AT060, AT064 and BT012) were then madein order to form GR5 and GR8, in accordance with what is shown in Table8 herein relating to the solutions GR5 and GR8. Specifically, AT064 andBT012 were mixed together to form GR5; and AT060 and BT012 were mixedtogether to form GR8 to result in the amounts of silver and zinc in eachbeing the same as what is shown in Table 8.

Once the solutions of GR5 and GR8 were formed, the cytotoxicity for eachwas measured. Specifically, as shown in FIG. 73A and FIG. 73B thecytotocicity of GR5 was determined. In this regard, the LD₅₀ for GR5,based on silver nanoparticle concentration, was 5.092; whereas the LD₅₀based on total nanoparticle concentration (i.e., both silver and zinc)was 15.44.

In comparison, FIG. 74A shows the LD₅₀, based on silver nanoparticleconcentration, for GR8, which was 4.874. Similarly, FIG. 74B shows theLD₅₀ equal to 18.05 regarding the total nanoparticle concentration(i.e., total of silver and zinc particles) in GR8.

The other inventive material in this Example 11, “PT001”, was made bythe following process. Electrode Set #1 was a 1, 5 combination.Electrode Set #2 was also a 1, 5 combination. There were no electrodesets at positions 2-8. Accordingly, the designation for this electrodecombination was a “11XXXXXX”. The composition of each of electrodes 1and 5 in both Electrode Sets #1 and #2 were high-purity platinum (i.e.,99.999%). Table 16a sets forth the specific run conditions for PT001.

Further, bar charts of the actual and target voltages for each electrodein each electrode set, are shown in FIG. 75. Accordingly, the datacontained in Table 16a, as well as in FIG. 75, give a completeunderstanding of the electrode design in each electrode set as well asthe target and actual voltages applied to each electrode for themanufacturing processes.

TABLE 16a Run ID: PT001 Flow Rate: 150 ml/min Target Distance DistanceAverage Voltage “c-c” “x” Voltage Set # Electrode # (kV) in/mm in/mm(kV) 7/177.8* 1 1a 1.90 .22/5.59 2.00 5a 1.37 N/A 1.51 8/203.2  2 1b0.78 .22/5.59 0.87 5b 0.19 N/A 0.18  57/1447.8** N/A N/A N/A N/A N/A N/AOutput Water Temperature 49 C. *Distance from water inlet to center offirst electrode set **Distance from center of last electrode set towater outlet

The solution PT001 was then treated as if it had an equivalent volume ofzinc-based nanoparticles equivalent to those present in BT012 (i.e., 23ppm zinc). In other words, a volume of about 150 ml of PT001 was addedto about 50 ml of AT064 to produce GR5* and a volume of about 170 ml ofPT001 was added to about 33 ml of AT060 to produce GR8*. Once mixed,these new material solutions (i.e., GR5* and GR8*) were allowed to sitfor 24 hours prior to being tested for cytotoxicity.

FIG. 76A shows that the LD₅₀ for GR5* was 8.794 (i.e., based on totalsilver nanoparticle concentration). This compares with an LD₅₀ forsilver alone in AT064 of 7.050; and an LD₅₀ for GR5 (based on silverconcentration alone) of 5.092.

Likewise, FIG. 76B shows the cytotoxicity of GR8* as a function ofsilver nanoparticle concentration. The LD₅₀ (i.e., based on silvernanoparticle concentration) for GR8* is 7.165. This compares directly toan LD₅₀ for AT060 of 9.610 and an LD₅₀ for GR8 (based on silverconcentration alone) of 4.874.

Accordingly, the LD₅₀ of each of GR5* and GR8* was higher than thecorresponding LD₅₀'s of GR5 and GR8, respectively (i.e., with regard tothe silver content in each of the mixes GR5 and GR8).

The biological efficacies against E. coli of each of GR5 and GR5* werethen compared. Specifically, FIG. 77A shows a Bioscreen reaction, runaccording to the procedures discussed above herein. In this Bioscreenreaction, it is clear that the performance of GR5 and GR5* weresubstantially identical.

Likewise, a comparison between the biological efficacy against E. coliwas also performed for GR8 and GR8*. This comparison is shown in FIG.77B. GR8 and GR8* both had substantially identical biologicalperformance.

Accordingly, this Example shows that cytotoxicity of solutions GR5 andGR8 can be lowered by utilizing the solution PT001 instead of BT012 ineach of the mixes GR5 and GR8. Moreover, such cytotoxicity is loweredwithout sacrificing biological efficacy against E. coli, as shown inFIGS. 77A and 77B.

However, it should be understood that other in vivo benefits can beobtained by the presence of, for example, the material corresponding toBT012 in the solutions GR5 and GR8.

Example 12 Comparison of Biological Performance of Two DifferentSilver-Based Nanoparticles/Nanoparticle Solutions by Adding VariableZinc Nanoparticles/Nanoparticle Solutions and Related Aging Study

The materials disclosed in Example 11, namely AT064 and AT060 and anequivalent to BT012 (i.e., BT013) were mixed together in varyingproportions to determine if any differences in biological efficacy couldbe observed (e.g., similar to the studies shown in FIGS. 49 and 50).However, in this study, biological efficacy as a function of timeelapsed between mixing the solutions together and testing for biologicalefficacy was investigated.

Specifically, FIG. 78A shows biological efficacy results of a variety ofmixtures of AT064 with BT013 wherein the amount of AT064 remains at aconstant ppm relative to the amount of BT013 added. Accordingly, thisresulted in an increasing sequence of zinc being added as follows 2 ppmZn, 4 ppm Zn, 8 ppm Zn and 13 ppm Zn. These differing amounts of Znadditions were achieved by a similar approach used for generating thedata associated with FIGS. 49 and 50. FIG. 78A clearly shows that thebiological performance of AT064 was enhanced by adding BT013. Note thatefficacy tests were begun immediately after mixing AT064 and BT013together. Specifically, FIG. 78A shows biological performance of thevarious silver-zinc mixtures wherein such mixtures were mixed as closein time as possible (Δt=0) to beginning the Bioscreen run. The 13 ppm Znadded showed great enhanced performance relative to AT064 as well as theother lower ppm zinc levels. However, only slight differences inperformance existed between 2 ppm, 4 ppm and 8 ppm Zn additions,relative to each other. These relative performances were greatlyenhanced in FIG. 78B.

Specifically, FIG. 78B shows a Δt=1, which corresponds to allowing theraw materials AT064 and BT013 to sit undisturbed after being mixedtogether for approximately 24 hours prior to being placed in theBioscreen test. Clear distinctions in biological efficacy are seenbetween all of the Zn ppm additions to AT064, with the 13 ppm stillperforming equal to the negative control after 0.8 days. Accordingly,enhanced performance by mixing of BT013 with AT064 was achieved byallowing a period of time to elapse after mixing, prior to biologicalefficacy testing.

FIG. 79A shows slightly different results from FIG. 78A. Particularly,FIG. 79A shows the changes in biological efficacy of AT060 when mixedwith 2 ppm Zn, 4 ppm Zn, 8 ppm Zn and 13 ppm Zn. In contrast to FIG.78A, the 2 ppm and 4 ppm zinc additions to AT060 did not show any changein biological efficacy after mixing together and conducting immediatebiological testing. Accordingly, with Δt=0 in this experiment, whichcorresponds to mixing AT060 with BT013 and immediately testing in theBioscreen, no enhancement in efficacy was observed for the addition of 2ppm and 4 ppm Zn. Slightly enhanced performance of AT060 was observedwith 8 ppm Zn and 13 ppm Zn.

However, the biological efficacy results are dramatically different inFIG. 79B. In this efficacy experiment, the components AT060 and BT013were allowed to sit together for Δt=1, which corresponds toapproximately 24 hours. After allowing the materials AT060 and BT013 tosit for approximately 24 hours, and then subsequent Bioscreen testingwas performed, a spread in efficacy, similar to that shown in FIG. 78B,was observed. Specifically, there are clear biological efficacydistinctions that exist between AT060 with additions of each of 2 ppm, 4ppm, 8 ppm and 13 ppm of Zn added thereto, respectively.

Additional biological efficacy tests were run to determine if additional“hold time” had any further enhancing effects. Specifically, the data inFIG. 79C correspond to a “hold time” of Δt=2 (i.e., approximately 48hours) prior to testing for efficacy changes of AT060 as a function ofincreasing Zn ppm concentration. It was determined that the efficacychanges shown in FIG. 79C were substantially identical to the efficacychanges shown in FIG. 79B. Accordingly, it is clear that reactions whichoccurred in FIG. 79B did not seem to occur to any greater extent between24 hours and 48 hours.

In an effort to clarify the differences in biological efficacy observedin FIG. 78A vs. FIG. 78B, and in FIG. 79A vs. FIGS. 79B and 79C, adynamic light scattering (“DLS”) experiment was performed, according tothe procedures discussed above herein.

Specifically, two sets of DLS tests were performed. The first test mixedtogether AT064 and BT013 in proportion to produce GR5 (i.e., about 50 mlof AT064 and about 150 ml of BT013). The second test mixed togetherAT060 and BT013 in proportion to produce GR8 (i.e., about 33 ml of AT060and about 170 ml of BT013).

The results of the DLS measurements as a function of time after mixingthe aforementioned materials together are shown in FIGS. 80 and 81.Specifically, FIGS. 80A-80F show DLS size measurements taken at sixdifferent times, namely, t=0; t=80 minutes; t=5 hours; t=5.5 hours; t=6hours; and t=21 hours. Similarly, FIGS. 81A-81E show DLS sizemeasurements taken at five different times, namely, t=0; t=80 minutes;t=4 hours; t=5 hours; and t=21 hours.

It is clear from the results shown in FIGS. 80 and 81, that one or morereaction(s) are occurring between AT064 and BT013; as well as one ormore reaction(s) occurring between AT060 and BT013. While the initialparticle sizes of AT064 and AT060 may be different, according to, forexample, the TEM photomicrographs of FIG. 43, discussed earlier herein,the concentration and nature of solutions containing Ag and solutionscontaining Zn are different in each of GR5 and GR8. In any event, DLSmeasurements of both mixtures comprising GR5 and GR8 show relativelylarge particle sizes being present. Perhaps some particle agglomentationmay be occurring. However, after a period of 5-6 hours, DLS measurementsindicate the detected particle sizes have significantly diminished.Further, after 21 hours, the DLS measurements suggest that the detectedparticle sizes were substantially equivalent.

Without wishing to be bound by any particular theory or explanation, itappears that particle size and biological performance (e.g., efficacyagainst E. coli) are related.

Example 13 The Effect of Input Water Temperature on the Manufacturingand Properties of Silver-Based Nanoparticles/Nanoparticle SolutionsAT110, AT109 and AT111 and Zinc-Based Nanoparticles/NanoparticleSolutions BT015, BT014 and BT016; and 50/50 Volumetric Mixtures Thereof

This Example utilizes essentially the same basic apparatus used to makethe solutions of Examples 1-5, however, this Example uses threedifferent temperatures of water input into the trough member 30.

Specifically: (1) water was chilled in a refrigerator unit until itreached a temperature of about 2° C. and was then pumped into the troughmember 30, as in Examples 1-5; (2) water was allowed to adjust toambient room temperature (i.e., 21° C.) and was then pumped into thetrough member 30, as in Examples 1-5; and (3) water was heated in ametal container until it was about 68° C. (i.e., for Ag-based solution)and about 66° C. (i.e., for Zn-based solution), and was then pumped intothe trough member 30, as in Examples 1-5.

The silver-based nanoparticle/nanoparticle solutions were allmanufactured using a set-up where Electrode Set #1 and Electrode Set #4both used a “1, 5” electrode configuration. All other Electrode Sets #2,#3 and #5-#8, used a “5, 5′” electrode configuration. These silver-basednanoparticle/nanoparticle solutions were made by utilizing 99.95% puresilver electrodes for each of electrodes 1 and/or 5 in each electrodeset.

Also, the zinc-based nanoparticles/nanoparticle solutions were allmanufactured with each of Electrode Sets #1-#8 each having a “1,5”electrode configuration. These zinc-based nanoparticles/nanoparticlesolutions also were made by utilizing 99.95% pure zinc electrodes forthe electrodes 1,5 in each electrode set.

Tables 17a-17f summarize electrode design, configuration, location andoperating voltages. As shown in Tables 17a-17c, relating to silver-basednanoparticle/nanoparticle solutions, the target voltages were set to alow of about 620 volts and a high of about 2,300 volts; whereas withregard to zinc-based solution production, Tables 17d-17f show the targetvoltages were set to a low of about 500 volts and a high of about 1,900volts.

Further, bar charts of the actual and target voltages for each electrodein each electrode set, are shown in FIGS. 82A-82F. Accordingly, the datacontained in Tables 17a-17f, as well as in FIGS. 82A-82F, give acomplete understanding of the electrode design in each electrode set aswell as the target and actual voltages applied to each electrode for themanufacturing processes.

TABLE 17a Cold Input Water (Ag) Run ID: AT110 Flow Rate: 200 ml/minTarget Distance Distance Average Voltage “c-c” “x” Voltage Set #Electrode # (kV) in/mm in/mm (kV)  7/177.8* 1 1a 2.35 0.22/5.59 2.34 5a2.00 N/A 2.01 8/203.2 2 5b 1.40 N/A 1.41  5b′ 1.51 N/A 1.51 8/203.2 3 5c1.23 N/A 1.22  5c′ 1.26 N/A 1.26 8/203.2 4 1d 1.37 0.19/4.83 1.37 5d0.99 N/A 1.00 9/228.6 5 5e 1.17 N/A 1.17  5e′ 0.62 N/A 0.62 8/203.2 6 5f0.63 N/A 0.63  5f′ 0.58 N/A 0.58 8/203.2 7 5g 0.76 N/A 0.76  5g′ 0.61N/A 0.64 8/203.2 8 5h 0.70 N/A 0.70  5h′ 0.94 N/A 0.96  8/203.2** InputWater Temp 2 C. Output Water Temp 70 C. *Distance from water inlet tocenter of first electrode set **Distance from center of last electrodeset to water outlet

TABLE 17b Room Temperature Input Water (Ag) Run ID: AT109 Flow Rate: 200ml/min Target Distance Distance Average Voltage “c-c” “x” Voltage Set #Electrode # (kV) in/mm in/mm (kV)  7/177.8* 1 1a 2.23 0.22/5.59 2.19 5a1.80 N/A 1.79 8/203.2 2 5b 1.26 N/A 1.19  5b′ 1.42 N/A 1.42 8/203.2 3 5c1.27 N/A 1.25  5c′ 1.30 N/A 1.30 8/203.2 4 1d 1.46 0.19/4.83 1.39 5d1.05 N/A 1.04 9/228.6 5 5e 1.15 N/A 1.14  5e′ 0.65 N/A 0.64 8/203.2 6 5f0.74 N/A 0.73  5f′ 0.69 N/A 0.69 8/203.2 7 5g 0.81 N/A 0.80  5g′ 0.65N/A 0.66 8/203.2 8 5h 0.80 N/A 0.79  5h′ 1.05 N/A 1.05  8/203.2** InputWater Temp 21 C. Output Water Temp 75 C. *Distance from water inlet tocenter of first electrode set **Distance from center of last electrodeset to water outlet

TABLE 17c Hot Input Water (Ag) Run ID: AT111 Flow Rate: 200 ml/minTarget Distance Distance Average Voltage “c-c” “x” Voltage Set #Electrode # (kV) in/mm in/mm (kV)  7/177.8* 1 1a 2.29 0.22/5.59 2.19 5a1.75 N/A 1.76 8/203.2 2 5b 1.39 N/A 1.39  5b′ 1.64 N/A 1.64 8/203.2 3 5c1.41 N/A 1.42  5c′ 1.49 N/A 1.48 8/203.2 4 1d 1.62 0.19/4.83 1.61 5d1.29 N/A 1.29 9/228.6 5 5e 1.41 N/A 1.42  5e′ 0.94 N/A 0.93 8/203.2 6 5f0.94 N/A 0.94  5f′ 0.91 N/A 0.91 8/203.2 7 5g 1.02 N/A 1.03  5g′ 0.88N/A 0.88 8/203.2 8 5h 0.95 N/A 0.95  5h′ 1.15 N/A 1.16  8/203.2** InputWater Temp 68 C. Output Water Temp 94 C. *Distance from water inlet tocenter of first electrode set **Distance from center of last electrodeset to water outlet

TABLE 17d Cold Input Water (Zn) Run ID: BT015 Flow Rate: 150 ml/minTarget Distance Distance Average Voltage “c-c” “x” Voltage Set #Electrode # (kV) in/mm in/mm (kV)  7/177.8* 1 1a 1.91 0.29/7.37 1.90 5a1.67 N/A 1.65 8/203.2 2 1b 1.07 0.22/5.59 1.11 5b 1.19 N/A 1.20 8/203.23 1c 0.89 0.22/5.59 0.85 5c 0.88 N/A 0.88 8/203.2 4 1d 0.98 0.15/3.811.08 5d 0.77 N/A 0.76 9/228.6 5 1e 1.31 0.22/5.59 1.37 5e 0.50 N/A 0.508/203.2 6 1f 1.07 0.22/5.59 1.07 5f 0.69 N/A 0.69 8/203.2 7 1g 0.790.22/5.59 0.79 5g 0.73 N/A 0.74 8/203.2 8 1h 0.61 0.15/3.81 0.60 5h 0.88N/A 0.85  8/203.2** Input Water Temp 2 C. Output Water Temp 63 C.*Distance from water inlet to center of first electrode set **Distancefrom center of last electrode set to water outlet

TABLE 17e Room Temperature Input Water (Zn) Run ID: BT014 Flow Rate: 150ml/min Target Distance Distance Average Voltage “c-c” “x” Voltage Set #Electrode # (kV) in/mm in/mm (kV)  7/177.8* 1 1a 1.82 0.29/7.37 1.79 5a1.58 N/A 1.57 8/203.2 2 1b 1.06 0.22/5.59 1.04 5b 1.14 N/A 1.14 8/203.23 1c 0.91 0.22/5.59 0.90 5c 0.84 N/A 0.85 8/203.2 4 1d 0.88 0.15/3.810.88 5d 0.71 N/A 0.73 9/228.6 5 1e 1.55 0.22/5.59 1.30 5e 0.50 N/A 0.508/203.2 6 1f 1.06 0.22/5.59 1.08 5f 0.72 N/A 0.72 8/203.2 7 1g 0.820.22/5.59 0.82 5g 0.76 N/A 0.76 8/203.2 8 1h 0.83 0.15/3.81 0.60 5h 0.92N/A 0.88  8/203.2** Input Water Temp 21 C. Output Water Temp 69 C.*Distance from water inlet to center of first electrode set **Distancefrom center of last electrode set to water outlet

TABLE 17f Hot Input Water (Zn) Run ID: BT016 Flow Rate: 150 ml/minTarget Distance Distance Average Voltage “c-c” “x” Voltage Set #Electrode # (kV) in/mm in/mm (kV)  7/177.8* 1 1a 1.87 0.29/7.37 1.81 5a1.62 N/A 1.62 8/203.2 2 1b 1.22 0.22/5.59 1.17 5b 1.27 N/A 1.23 8/203.23 1c 1.06 0.22/5.59 1.00 5c 1.02 N/A 1.00 8/203.2 4 1d 1.13 0.15/3.811.12 5d 0.94 N/A 0.92 9/228.6 5 1e 1.46 0.22/5.59 1.43 5e 0.67 N/A 0.698/203.2 6 1f 1.25 0.22/5.59 1.23 5f 0.89 N/A 0.89 8/203.2 7 1g 0.950.22/5.59 0.95 5g 0.87 N/A 0.83 8/203.2 8 1h 0.75 0.15/3.81 0.71 5h 1.01N/A 0.99  8/203.2** Input Water Temp 66 C. Output Water Temp 82 C.*Distance from water inlet to center of first electrode set **Distancefrom center of last electrode set to water outlet

Once each of the silver-based nanoparticle/nanoparticle solutions AT110,AT109 and AT111, as well as the zinc-based nanoparticle/nanoparticlesolutions BT015, BT014 and BT016 were manufactured, these six solutionswere mixed together to make nine separate 50/50 volumetric mixtures.Reference is made to Table 17g which sets forth a variety of physicaland biological characterization results for the six “raw materials” aswell as the nine mixtures made therefrom.

TABLE 17g Predominant DLS Mass Time (hours) to Zeta DistributionRelative Bacteria Growth PPM PPM Potential DLS Peak Bioscreen BeginningAg Zn (Avg) pH % Transmission (Radius in nm) Performance (1.0 McFarland)Cold Ag (AT 110) 49.4 N/A −8.4 3.8  40% 41.8 4.0 3.30 RT Ag (AT 109)39.5 N/A −19.7 4.5  5%   46.3 * 2.0 3.00 Hot Ag (AT 111) 31.1 N/A −38.25.2  4%   15.6 * 3.3 3.50 Cold Zn (BT 015) N/A 24.1 19.2 2.8 100% 46.20.0 0.00 RT Zn (BT 014) N/A 24.6 11.2 2.9 100% 55.6 0.0 0.00 Hot Zn (BT016) N/A 17.7 11.9 3.1 100%   12.0 * 0.0 0.00 Cold Ag/Cold Zn 24.3 11.926.4 3.0 100%   25.2 * 2.7 5.25 Cold Ag/RT Zn 24.2 12.0 25.2 3.3 100%55.0 9.0 17.00 Cold Ag/Hot Zn 24.3 8.6 24.5 3.3 100%   28.3 * 9.0 16.50RT Ag/Cold Zn 19.9 11.8 23.0 3.1 100% 58.6 11.0 16.25 RT Ag/RT Zn 20.212.4 18.3 3.3 100%  1.5 6.3 12.00 RT Ag/Hot Zn 20.2 8.6 27.0 3.4 100%52.9 4.7 5.00 Hot Ag/Cold Zn 14.0 12.0 24.6 3.2 100% 51.4 11.7 17.25 HotAg/RT Zn 14.2 12.0 13.7 3.3 100% 48.7 7.3 13.45 Hot Ag/Hot Zn 15.0 8.57.2 3.4 100% 44.6 9.7 16.75 * DLS data varies significantly suggestingvery small particulate and/or significant ionic character

Specifically, for example, in reference to the first mixture listed inTable 17g, that mixture is labeled as “Cold Ag/Cold Zn”. Similarly, thelast of the mixtures referenced in Table 17g is labeled “Hot Ag/Hot Zn”.“Cold Ag” or “Cold Zn” refers to the input water temperature into thetrough member 30 being about 2° C. “RT Ag” or “RT Zn” refers to theinput water temperature being about 21° C. “Hot Ag” refers to refers tothe input water temperature being about 68° C.; and “Hot Zn” refers tothe input water temperature to the trough member 30 being about 66° C.

The physical parameters reported for the individual raw materials, aswell as for the mixtures, include “PPM Ag” and “PPM Zn”. These ppm's(parts per million) were determined by the Atomic AbsorptionSpectroscopy techniques discussed above herein in Example 6. It isinteresting to note that the measured PPM of the silver component in thesilver-based nanoparticle/nanoparticle solutions was higher when theinput temperature of the water into the trough member 30 was lower(i.e., Cold Ag (AT110) corresponds to an input water temperature of 2°C. and a measured PPM of silver of 49.4). In contrast, when the inputtemperature of the water used to make sample AT111 was increased to 68°C. (i.e., the “Hot Ag”), the measured amount of silver decreased to 31.1ppm (i.e., a change of almost 20 ppm). Accordingly, when mixtures weremade utilizing the raw material “Cold Ag” versus “Hot Ag”, the PPMlevels of the silver in the resulting mixtures varied.

Each of the nine mixtures formulated were each approximately 50% byvolume of the silver-based nanoparticle solution and 50% by volume ofthe zinc-based nanoparticle solution. Thus, whenever “Hot Ag” solutionwas utilized, the resulting PPM in the mixture would be roughly half of31.1 ppm; whereas when the “Cold Ag” solution was utilized the silverPPM would be roughly half of 49.4 ppm.

The zinc-based nanoparticle/nanoparticle solutions behaved similarly tothe silver-based nanoparticle/nanoparticle solutions in that themeasured PPM of zinc decreased as a function of increasing water inputtemperature, however, the percent decrease was less. Accordingly,whenever “Cold Zn” was utilized as a 50 volume percent component in amixture, the measured zinc ppm in the mixtures was larger than themeasured zinc ppm when “Hot Zn” was utilized.

Table 17g includes a third column, entitled, “Zeta Potential (Avg)”.“Zeta potential” is known as a measure of the electo-kinetic potentialin colloidal systems. Zeta potential is also referred to as surfacecharge on particles. Zeta potential is also known as the potentialdifference that exists between the stationary layer of fluid and thefluid within which the particle is dispersed. A zeta potential is oftenmeasured in millivolts (i.e., mV). The zeta potential value ofapproximately 25 mV is an arbitrary value that has been chosen todetermine whether or not stability exists between a dispersed particlein a dispersion medium. Thus, when reference is made herein to “zetapotential”, it should be understood that the zeta potential referred tois a description or quantification of the magnitude of the electricalcharge present at the double layer.

The zeta potential is calculated from the electrophoretic mobility bythe Henry equation:

$U_{E} = \frac{2ɛ\; {{zf}({ka})}}{3\eta}$

where z is the zeta potential, U_(E) is the electrophoretic mobility, Eis a dielectric constant, η is a viscosity, ƒ(ka) is Henry's function.For Smoluchowski approximation ƒ(ka)=1.5.

Electrophoretic mobility is obtained by measuring the velocity of theparticles in an applied electric field using Laser Doppler Velocimetry(“LDV”). In LDV the incident laser beam is focused on a particlesuspension inside a folded capillary cell and the light scattered fromthe particles is combined with the reference beam. This produces afluctuating intensity signal where the rate of fluctuation isproportional to the speed of the particles (i.e. electrophoreticmobility).

In this Example, a Zeta-Sizer “Nano-ZS” produced by Malvern Instrumentswas utilized to determine zeta potential. For each measurement a lmlsample was filled into clear disposable zeta cell DTS1060C. DispersionTechnology Software, version 5.10 was used to run the Zeta-Sizer and tocalculate the zeta potential. The following settings were used:dispersant—water, temperature—25° C., viscosity—0.8872 cP, refractionindex—1.330, dielectric constant—78.5, approximation model—Smoluchowski.One run of hundred repetitions was performed for each sample.

Table 17g shows clearly that for the silver-basednanoparticle/nanoparticle solutions the zeta potential increased innegative value with a corresponding increasing input water temperatureinto the trough member 30. In contrast, the Zeta-Potential for thezinc-based nanoparticle/nanoparticle solutions was positive anddecreased slightly in positive value as the input temperature of thewater into the trough member 30 increased.

It is also interesting to note that the zeta potential for all nine ofthe mixtures made with the aforementioned silver-basednanoparticle/nanoparticle solutions and zinc-basednanoparticle/nanoparticle solutions raw materials were positive withdifferent degrees of positive values being measured.

The fourth column in Table 17g reports the measured pH. The pH wasmeasured for each of the raw material solutions, as well as for each ofthe mixtures. These pH measurements were made in accordance with theteachings for making pH measurements in Examples 1-5. It is interestingto note that the pH of the silver-based nanoparticle/nanoparticlesolutions changed significantly as a function of the input watertemperature into the trough member 30 starting with a low of 3.8 for thecold input water (i.e., 2° C.) and increasing to a value of 5.2 for thehot water input (i.e., 68° C.). In contrast, while the measured pH foreach of three different zinc-based nanoparticle/nanoparticle solutionswere, in general, significantly lower than any of the silver-basednanoparticle/nanoparticle solutions pH measurements, the pH did not varyas much in the zinc-based nanoparticle/nanoparticle solutions.

The pH values for each of the nine mixtures were much closer to the pHvalues of the zinc-based nanoparticle/nanoparticle solutions, namely,ranging from a low of about 3.0 to a high of about 3.4.

The fifth column in Table 17g reports “DLS % Transmission”. The “DLS”corresponds to Dynamic Light Scattering. Specifically, the DLSmeasurements were made according to the DLS measuring techniquesdiscussed above herein (e.g., Example 7). The “% Transmission” isreported in Table 17g because it is important to note that lower numberscorrespond to a lesser amount of laser intensity being required toreport detected particle sizes (e.g., a reduced amount of laser light isrequired to interact with species when such species have a larger radiusand/or when there are higher amounts of the species present).Accordingly, the DLS % Transmission values for the three silver-basednanoparticle/nanoparticle solutions were lower than all other %Transmission values. Moreover, a higher “% of Transmission” number(i.e., 100%) is indicative of very small nanoparticles and/orsignificant ionic character present in the solution (e.g., at least whenthe concentration levels or ppm's of both silver and zinc are as low asthose reported herein).

The next column entitled, “Predominant DLS Mass Distribution Peak(Radius in nm)” reports numbers that correspond to the peak in theGaussian curves obtained in each of the DLS measurements. For example,these reported peak values come from Gaussian curves similar to the onesreported in FIGS. 62, 80 and 81. For the sake of brevity, the entirecurves have not been included as FIGs. in this Example. However,wherever an “*” occurs, that “*” is intended to note that whenconsidering all of the DLS reported data, it is possible that thesolutions may be largely ionic in character, or at least themeasurements from the DLS machine are questionable. It should be notedthat at these concentration levels, in combination with small particlesizes and/or ionic character, it is often difficult to get an absolutelyperfect DLS report. However, the relative trends are very informative.

The last two columns in Table 17g summarize detailed microbiologicalstudies. In this regard, E. coli bacteria were tested in a Bioscreenapparatus. The procedures for testing were similar to those proceduresdiscussed in Examples 1-5 herein. Specifically, FIG. 82G shows a changein optical density as a function of time, wherein the main differencebetween these Bioscreen results and those reported elsewhere herein isthat the reported times of “t=0” (i.e., 00:00:00) is actually after 5hours of incubation of the E. coli in a 1.0 McFarland.

The column entitled “Relative Bioscreen Performance” is a merit ranking,wherein the higher numbers correspond to the highest performing rawmaterials and solutions relative to each other. In this regard, thenumbers 11 and 11.7 corresponding to “RT Ag/Cold Zn” and “Hot Ag/ColdZn”, respectively were the best performers, based on this ranking.However, in order to define the performances even more particularly, thecolumn entitled, “Time (hours) to Bacteria Growth Beginning (1.0McFarland)” shows that the “Cold Ag”, “RT Ag” and “Hot Ag” allowbacteria to begin to grow between 3 and 3.5 hours; the “Cold Zn”, “RTZn” and “Hot Zn” did not inhibit bacterial growth at all (i.e., thebacterial growth curves substantially corresponded to control growthcurves); and the nine different mixtures provided varying times when thebacteria begin to grow with the two worst performing mixtures being“Cold Ag/Cold Zn” (i.e., 5.25 hours) and “RT Ag/Hot Zn” (i.e., 5.00hours); in contrast to the better performing mixtures showing growthtimes beginning around 16 and 17 hours.

Without wishing to be bound by any particular theory or explanation, itis clear that the input temperature of the liquid into the trough member30 does have an effect on the inventive solutions made according to theteachings herein. Specifically, not only are amounts of components(e.g., ppm) affected by water input temperature, but physical propertiesand biological performance are also affected. Thus, control of watertemperature, in combination with control of all of the other inventiveparameters discussed herein, can permit a variety of particle sizes tobe achieved, differing zeta potentials to be achieved, different pH's tobe achieved and corresponding different performance (e.g., biologicalperformances) to be achieved.

Example 14 Manufacturing Gold-Based Nanoparticles/Nanoparticle SolutionsGT032, GT031 and GT019

This Example utilizes essentially the same basic apparatus used to makethe solutions of Examples 1-5, however, this Example use gold electrodesfor the 8 electrode sets. In this regard, Tables 18a-18c set forthpertinent operating parameters associated with each of the 16 electrodesin the 8 electrode sets utilized to make gold-basednanoparticles/nanoparticle solutions.

TABLE 18a Cold Input Water (Au) Run ID: GT032 Flow Rate: 90 ml/minTarget Distance Distance Average Voltage “c-c” “x” Voltage Set #Electrode # (kV) in/mm in/mm (kV)  7/177.8* 1 1a 1.6113 0.22/5.59 1.655a 0.8621 N/A 0.84 8/203.2 2 5b 0.4137 N/A 0.39  5b′ 0.7679 N/A 0.768/203.2 3 5c 0.491 N/A 0.49  5c′ 0.4816 N/A 0.48 8/203.2 4 1d 0.4579 N/A0.45 5d 0.6435 N/A 0.60 9/228.6 5 5e 0.6893 N/A 0.67  5e′ 0.2718 N/A0.26 8/203.2 6 5f 0.4327 N/A 0.43  5f′ 0.2993 N/A 0.30 8/203.2 7 5g0.4691 N/A 0.43  5g′ 0.4644 N/A 0.46 8/203.2 8 5h 0.3494 N/A 0.33  5h′0.6302 N/A 0.61  8/203.2** Output Water Temperature 65 C. *Distance fromwater inlet to center of first electrode set **Distance from center oflast electrode set to water outlet

TABLE 18b 38.3 mg/L of NaHCO₃ (Au) Run ID: GT031 Flow Rate: 90 ml/minTarget Distance Distance Average Voltage “c-c” “x” Voltage Set #Electrode # (kV) in/mm in/mm (kV)  7/177.8* 1 1a 1.7053 0.22/5.59 1.695a 1.1484 N/A 1.13 8/203.2 2 5b 0.6364 N/A 0.63  5b′ 0.9287 N/A 0.928/203.2 3 5c 0.7018 N/A 0.71  5c′ 0.6275 N/A 0.62 8/203.2 4 5d 0.6798N/A 0.68 5d 0.7497 N/A 0.75 9/228.6 5 5e 0.8364 N/A 0.85  5e′ 0.4474 N/A0.45 8/203.2 6 5f 0.5823 N/A 0.59  5f′ 0.4693 N/A 0.47 8/203.2 7 5g0.609 N/A 0.61  5g′ 0.5861 N/A 0.59 8/203.2 8 5h 0.4756 N/A 0.48  5h′0.7564 N/A 0.76  8/203.2** Output Water Temperature 64 C. *Distance fromwater inlet to center of first electrode set **Distance from center oflast electrode set to water outlet

TABLE 18c 45 mg/L of NaCl (Au) Run ID: GT019 Flow Rate: 90 ml/min TargetDistance Distance Average Voltage “c-c” “x” Voltage Set # Electrode #(kV) in/mm in/mm (kV)  7/177.8* 1 1a 1.4105 0.22/5.59 1.41 5a 0.8372 N/A0.87 8/203.2 2 5b 0.3244 N/A 0.36  5b′ 0.4856 N/A 0.65 8/203.2 3 5c0.3504 N/A 0.37  5c′ 0.3147 N/A 0.36 8/203.2 4 5d 0.3526 N/A 0.37 5d0.4539 N/A 0.50 9/228.6 5 5e 0.5811 N/A 0.60  5e′ 0.2471 N/A 0.278/203.2 6 5f 0.3624 N/A 0.38  5f′ 0.2905 N/A 0.31 8/203.2 7 5g 0.3387N/A 0.36  5g′ 0.3015 N/A 0.33 8/203.2 8 5h 0.2995 N/A 0.33  5h′ 0.5442N/A 0.57  8/203.2** Output Water Temperature 77 C. *Distance from waterinlet to center of first electrode set **Distance from center of lastelectrode set to water outlet

Further, FIGS. 83A, 83B and 83C show bar charts of each of the averageactual voltages applied to each of the 16 electrodes in the 8 electrodesets. It should be noted that the electrode configuration was slightlydifferent than the electrode configuration in each of Examples 1-5.Specifically, Table 18a shows that a “1,5” electrode configuration wasutilized for Electrode Set #1 and Electrode Set #4 and all other setswere of the 5/5 configuration; whereas Tables 18b and 18c show thatElectrode Set #1 was the only electrode set utilizing the 1/5configuration, and all other sets were of the 5/5 configuration.

Additionally, the following differences in manufacturing set-up werealso utilized:

-   -   i) GT032: The input water 3 into the trough member 30 was        chilled in a refrigerator unit until it reached a temperature of        about 2° C. and was then pumped into the trough member 30, as in        Examples 1-5;    -   ii) GT031: A processing enhancer was added to the input water 3        prior to the water 3 being input into the trough member 30.        Specifically, about 0.145 grams/gallon (i.e., about 38.3        mg/liter) of sodium hydrogen carbonate (“soda”), having a        chemical formula of NaHCO₃, was added to and mixed with the        water 3. The soda was obtained from Alfa Aesar and the soda had        a formula weight of 84.01 and a density of 2.159 g/cm³ (i.e.,        stock #14707, lot D15T043).    -   iii) GT019: A processing enhancer was added to the input water 3        prior to the water 3 being input into the trough member 30.        Specifically, about 0.17 grams/gallon (i.e., about 45 mg/liter)        of sodium chloride (“salt”), having a chemical formula of NaCl,        was added to and mixed with the water 3. The salt was obtained        from Fisher Scientific (lot #080787) and the salt had a formula        weight of 58.44 and an actual analysis as follows:

Assay    100% Barium (BA) Pass Test Bromide <0.010% Calcium 0.0002%Chlorate & Nitrate <0.0003%  Heavy Metals (AS PB) <5.0 ppmIdentification Pass Test Insoluble Water <0.001% Iodide 0.0020% Iron(FE) <2.0 ppm Magnesium <0.0005%  Ph 5% Soln @ 25 Deg C. 5.9 Phosphate(PO4) <5.0 ppm Potassium (K) <0.003% Sulfate (SO4) <0.0040% 

TABLE 18d Predominant DLS Mass Zeta DLS Distribution Color Potential %Peak of PPM (Avg) pH Transmission (Radius in nm) Solution GT032 0.4−19.30 3.29 11.7% 3.80 Clear GT031 1.5 −29.00 5.66 17.0% 0.78 PurpleGT019 6.1 ** ** ** ** Pink **Values not measured

Table 18d summarizes the physical characteristics results for each ofthe three solutions GT032, GT031 and GT019. Full characterization ofGT-019 was not completed, however, it is clear that under the processingconditions discussed herein, both processing enhancers (i.e., soda andsalt) increase the measured ppm of gold in the solutions GT-031 andGT-019 relative to GT032.

Example 15 Y-Shaped Trough Member 30

This Example utilized a different apparatus from those used to make thesolutions in Examples 1-5, however, this Example utilized similartechnical concepts to those disclosed in the aforementioned Examples. Inreference to FIG. 84A, two trough member portions 30 a and 30 b, eachhaving a four electrode set, were run in parallel to each other andfunctioned as “upper portions” of the Y-shaped trough member 30. A firstZn-based solution was made in trough member 30 a and a second Ag-basedsolution was made substantially simultaneously in trough member 30 b.

Once the solutions made in trough members 30 a and 30 b had beenmanufactured, these solutions were then processed in three differentways, namely:

(i) The Zn-based and Ag-based solutions were mixed together at the point30 d and flowed to the base portion 30 o of the Y-shaped trough member30 immediately after being formed in the upper portions, 30 a and 30 b,respectively. No further processing occurred in the base portion 30 o;

(ii) The Zn-based and Ag-based solutions made in trough members 30 a and30 b were mixed together after about 24 hours had passed aftermanufacturing each solution in each upper portion trough member 30 a and30 b (i.e., the solutions were separately collected from each troughmember 30 a and 30 b prior to being mixed together); and

(iii) The solutions made in trough members 30 a and 30 b were mixedtogether in the base portion 30 o of the y-shaped trough member 30substantially immediately after being formed in the upper portions 30 aand 30 b, and were thereafter substantially immediately processed in thebase portion 30 o of the trough member 30 by another four electrode set.

Table 19a summarizes the electrode design, configuration, location andoperating voltages for each of trough members 30 a and 30 b (i.e., theupper portions of the trough member 30) discussed in this Example.Specifically, the operating parameters associated with trough member 30a were used to manufacture a zinc-based nanoparticle/nanoparticlesolution; whereas the operating parameters associated with trough member30 b were used to manufacture a silver-based nanoparticle/nanoparticlesolution. Once these silver-based and zinc-based solutions weremanufactured, they were mixed together substantially immediately at thepoint 30 d and flowed to the base portion 30 o. No further processingoccurred.

TABLE 19a Y-shaped trough target voltage tables, for upper portions 30aand 30b Run ID: YT-002

*Distance from water inlet to center of first electrode set **Distancefrom center of last electrode set to water outlet

Table 19b summarizes the electrode design, configuration, location andoperating voltages for each of trough members 30 a and 30 b (i.e., theupper portions of the trough member 30) discussed in this Example.Specifically, the operating parameters associated with trough member 30a were used to manufacture a zinc-based nanoparticle/nanoparticlesolution; whereas the operating parameters associated with trough member30 b were used to manufacture a silver-based nanoparticle/nanoparticlesolution. Once these silver-based and zinc-based solutions weremanufactured, they were separately collected from each trough member 30a and 30 b and were not mixed together until about 24 hours had passed.In this regard, each of the solutions made in 30 a and 30 b werecollected at the outputs thereof and were not allowed to mix in the baseportion 30 o of the trough member 30, but were later mixed in anothercontainer.

TABLE 19b Y-shaped trough target voltage tables, for upper portions 30aand 30b Run IDs: YT-003/YT-004

*Distance from water inlet to center of first electrode set **Distancefrom center of last electrode set to water outlet ***Mixed togetherafter 24 hours (YT-005)

Table 19c summarizes the electrode design, configuration, location andoperating voltages for each of trough members 30 a and 30 b (i.e., theupper portions of the trough member 30) discussed in this Example.Specifically, the operating parameters associated with trough member 30a were used to manufacture a zinc-based nanoparticle/nanoparticlesolution; whereas the operating parameters associated with trough member30 b were used to manufacture a silver-based nanoparticle/nanoparticlesolution. Once these silver-based and zinc-based solutions weremanufactured, they were mixed together substantially immediately at thepoint 30 d and flowed to the base portion 30 o and the mixture wassubsequently processed in the base portion 30 o of the trough member 30.In this regard, Table 19c shows the additional processing conditionsassociated with the base portion 30 o of the trough member 30.Specifically, once again, electrode design, configuration, location andoperating voltages are shown.

TABLE 19c Y-shaped trough target voltage tables, for upper portions 30aand 30b Run ID: YT-001

*Distance from water inlet to center of first electrode set **Distancefrom center of last electrode set to water outlet

Table 19d shows a summary of the physical and biologicalcharacterization of the materials made in accordance with this Example15.

TABLE 19d (Y-shaped trough summary) Predominant DLS Mass Time to ZetaDLS Distribution Bacteria Potential % Peak Growth PPM Ag PPM Zn (Avg) pHTransmission (Radius in nm) Beginning YT-002BA 21.7 11.5 12.0 3.25 100%50.0 12.50 YT-003BX N/A 23.2 −13.7 2.86 100% 60.0 0.00 YT-004XA 41.4 N/A−26.5 5.26  40% 9.0 14.00 YT-005 21.0 11.0 2.6 3.10  25% 70.0 15.25YT-001BAB 22.6 19.5 −0.6 3.16 100% 60.0 15.50

Example 16 Plasma Irradiance and Characterization

This Example provides a spectrographic analysis of various adjustableplasmas 4, all of which were formed in air, according to the teachingsof the inventive concepts disclosed herein. Example 9 herein utilized asingle spectrometer (i.e., photon control silicon CCD Spectrometer 500)to analyze a variety of plasmas (i.e., collect spectral information inthe 200-1090 nm range), including spectral information for plasmas madein different atmospheres. In this Example, three different spectrometershaving greater sensitivities than the spectrometer used in Example 9were used to collect similar spectral information. Further,spectrographic analysis was conducted on several plasmas, wherein theelectrode member 1 comprised a variety of different metal compositions.Different species in the plasmas 4, as well as different intensities ofsome of the species, were observed. The presence/absence of such speciescan affect (e.g., positively and negatively) processing parameters andproducts made according to the teachings herein.

In this regard, FIG. 85 shows a schematic view, in perspective, of theexperimental setup used to collect emission spectroscopy informationfrom the adjustable plasmas 4 utilized herein.

Specifically, the experimental setup for collecting plasma emission data(e.g., irradiance) is depicted in FIG. 85. In general, threespectrometers 520, 521 and 522 receive emission spectroscopy datathrough a UV optical fiber 523 which transmits collimated spectralemissions collected by the assembly 524, along the path 527. Theassembly 524 can be vertically positioned to collect spectral emissionsat different vertical locations within the adjustable plasma 4 by movingthe assembly 524 with the X-Z stage 525. Accordingly, thepresence/absence and intensity of plasma species can be determined as afunction of interrogation location within the plasma 4. The output ofthe spectrometers 520, 521 and 522 is analyzed by appropriate softwareinstalled in the computer 528. All irradiance data was collected throughthe hole 531 which was positioned to be approximately opposite to thenon-reflective material 530. The bottom of the hole 531 was located atthe top surface of the liquid 3. More details of the apparatus forcollecting emission radiance follows below.

The assembly 524 contained one UV collimator (LC-10U) with a refocusingassembly (LF-10U100) for the 170-2400 nm range. The assembly 524 alsoincluded an SMA female connector made by Multimode Fiber Optics, Inc.Each LC-10U and LF-10U100 had one UV fused silica lens associatedtherewith. Adjustable focusing was provided by LF-10U100 at about 100 mmfrom the vortex of the lens in LF-10U100 also contained in the assembly524.

The collimator field of view at both ends of the adjustable plasma 4 wasabout 1.5 mm in diameter as determined by a 455 μm fiber core diametercomprising the solarization resistant UV optical fiber 523 (180-900 nmrange and made by Mitsubishi). The UV optical fiber 523 was terminatedat each end by an SMA male connector (sold by Ocean Optics;QP450-1-XSR).

The UV collimator-fiber system 523 and 524 provided 180-900 nm range ofsensitivity for plasma irradiance coming from the 1.5 mm diameter plasmacylinder horizontally oriented in different locations in the adjustableplasma 4.

The X-Z stage 525 comprised two linear stages (PT1) made by ThorlabsInc., that hold and control movement of the UV collimator 524 along theX and Z axes. It is thus possible to scan the adjustable plasma 4horizontally and vertically, respectively.

Emission of plasma radiation collected by UV collimator-fiber system523, 524 was delivered to either of three fiber coupled spectrometers520, 521 or 522 made by StellarNet, Inc. (i.e., EPP2000-HR for 180-295nm, 2400g/mm grating, EPP2000-HR for 290-400 nm, 1800g/mm grating, andEPP2000-HR for 395-505 nm, 1200g/mm grating). Each spectrometer 520, 521and 522 had a 7 μm entrance slit, 0.1 nm optical resolution and a 2048pixel CCD detector. Measured instrumental spectral line broadening is0.13 nm at 313.1 nm.

Spectral data acquisition was controlled by SpectraWiz software forWindows/XP made by StellarNet. All three EPP2000-HR spectrometers 520,521 and 522 were interfaced with one personal computer 528 equipped with4 USB ports. The integration times and number of averages for variousspectral ranges and plasma discharges were set appropriately to provideunsaturated signal intensities with the best possible signal to noiseratios. Typically, spectral integration time was order of 1 second andnumber averaged spectra was in range 1 to 10. All recorded spectra wereacquired with subtracted optical background. Optical background wasacquired before the beginning of the acquisition of a corresponding setof measurements each with identical data acquisition parameters.

Each UV fiber-spectrometer system (i.e., 523/520, 523/521 and 523/522)was calibrated with an AvaLight-DH-CAL Irradiance Calibrated LightSource, made by Avantes (not shown). After the calibration, all acquiredspectral intensities were expressed in (absolute) units of spectralirradiance (mW/m²/nm), as well as corrected for the nonlinear responseof the UV-fiber-spectrometer. The relative error of the AvaLight-DH-CALIrradiance Calibrated Light Source in 200-1100 nm range is not higherthan 10%.

Alignment of the field of view of the UV collimator assembly 524relative to the tip 9 of the metal electrode 1 was performed before eachset of measurements. The center of the UV collimator assembly 524 fieldof view was placed at the tip 9 by the alignment of two linear stagesand by sending a light through the UV collimator-fiber system 523, 524to the center of each metal electrode 1.

The X-Z stage 525 was utilized to move the assembly 524 into roughly ahorizontal, center portion of the adjustable plasma 4, while being ableto move the assembly 524 vertically such that analysis of the spectralemissions occurring at different vertical heights in the adjustableplasma 4 could be made. In this regard, the assembly 524 was positionedat different heights, the first of which was located as close aspossible of the tip 9 of the electrode 1, and thereafter moved away fromthe tip 9 in specific amounts. The emission spectroscopy of the plasmaoften did change as a function of interrogation position, as shown inFIGS. 86-89 herein.

For example, FIGS. 86A-86D show the irradiance data associated with asilver (Ag) electrode 1 utilized to form the adjustable plasma 4. Eachof the aforementioned FIG. 86 show emission data associated with threedifferent vertical interrogation locations within the adjustable plasma4. The vertical position “0” (0 nm) corresponds to emission spectroscopydata collected immediately adjacent to the tip 9 of the electrode 1; thevertical position “ 1/40” (0.635 nm) corresponds to emissionspectroscopy data 0.635 mm away from the tip 9 and toward the surface ofthe water 3; and the vertical position “ 3/20” (3.81 mm) corresponds toemission spectroscopy data 3.81 mm away from the tip 9 and toward thesurface of the water 3.

Table 20a shows specifically each of the spectral lines identified inthe adjustable plasma 4 when a silver electrode 1 was utilized to createthe plasma 4.

TABLE 20a λ meas. λ tab. λ meas. −λ tab. En Em Amn Transition (nm) (nm)(nm) (1/cm) (1/cm) gn gm (1/s) Ag || 5s ³D₃-5p ³D₃ 211.382 211.40000.0180 39168.032 86460.65 7 7 3.26E8 NO A²Σ⁺-X²Π γ-system: (1-0) 214.7214.7000 0.0000 Ag || 5s ³D₂-5p ³D₃ 218.676 218.6900 0.0140 40745.33586460.65 5 7 Ag || 5s ¹D₂-5p ³D₂ 222.953 222.9800 0.0270 46049.02990887.81 5 5 Ag || 5s ³D₃-5p ³F₄ 224.643 224.67 0.0270 39167.98683669.614 7 9 3.91E8 Ag || 5s ³D₃-5p ³P₁ 224.874 224.9 0.0260 40745.33585200.721 7 5 2.95E8 NO A²Σ⁺-X²Π γ-system: (0-0) 226.9 226.8300 −0.0700Ag || 5s ¹D₂-5p ¹P₁ 227.998 228.02 0.0220 46049.029 89895.502 5 3 1.39E8Ag || 5s ³D₁-5p ¹D₂ 231.705 231.7700 0.0650 43742.7 86888.06 3 5 Ag ||5s ¹D₂-5p ¹F₃ 232.029 232.0500 0.0210 46049.029 89134.688 5 7 2.74E8 Ag|| 5s ³D₃-5p ³F₃ 232.468 232.5100 0.0420 39167.986 82171.697 7 7 0.72E8Ag || 5s ³D₂-5p ³P₁ 233.14 233.1900 0.0500 40745.335 83625.479 5 32.54E8 NO A²Σ⁺-X²Π γ-system: (0-1) 236.3 236.2100 −0.0900 Ag || 5s³D₂-5p ³F₃ 241.323 241.3000 −0.0230 40745.335 82171.697 5 7 2.21E8 Ag ||5s ³D₃-5p ³P₂ 243.781 243.7700 −0.0110 39167.986 80176.425 7 5 2.88E8 Ag|| 5s ¹D₂-5p ¹D₂ 244.793 244.8000 0.0070 46049.029 86888.06 5 5 NOA²Σ⁺-X²Π γ-system: (0-2) 247.1 246.9300 −0.1700 NO A²Σ⁺-X²Π γ-system:(0-3) 258.3 258.5300 0.2300 NO A²Σ⁺-X²Π γ-system: (1-1) 267.1 267.0600−0.0400 NO A²Σ⁺-X²Π γ-system: (0-4) 271 271.1400 0.1400 OH A²Σ-X²Π (1-0)281.2 281.2000 0.0000 OH A²Σ-X²Π (1-0) 282 281.9600 −0.0400 N₂(C³Π_(u)-B³Π_(g)) 2⁺-system (4-2) 295.32 295.3300 0.0100 N₂(C³Π_(u)-B³Π_(g)) 2⁺-system (3-1) 296.2 296.1900 −0.0100 N₂(C³Π_(u)-B³Π_(g)) 2⁺-system (2-0) 297.7 297.7000 0.0000 OH A²Σ-X²Π:(0-0) 306.537 306.4600 −0.0770 OH A²Σ-X²Π: (0-0) 306.776 306.8400 0.0640OH A²Σ-X²Π: (0-0) 307.844 307.8700 0.0260 OH A²Σ-X²Π: (0-0) 308.986309.0700 0.0840 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system (2-1) 313.057 313.15640.0994 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system (1-0) 316 315.8700 −0.1300 Cu |3d¹⁰ (¹S) 4s ²S_(1/2) - 3d¹⁰(¹S) 4p ²P⁰ _(3/2) 324.754 324.7800 0.0260 030783.686 2 4 1.37E+8 Ag | 4d¹⁰(¹S) 5s ²S_(1/2) - 4d¹⁰(¹S) 5p ²P⁰ _(3/2)328.068 328.1200 0.0520 0 30472.703 2 4 1.47E+8 O₂ (B³Σ⁻ _(u)-X³Σ⁻ _(g))(0-14) 337 337.0800 0.0800 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system (0-0) 337.1337.1400 0.0400 Ag | 4d¹⁰(¹S) 5s ²S_(1/2) - 4d¹⁰(¹S) 5p ²P⁰ _(1/2)338.2887 338.3500 0.0613 0 29552.061 2 2 1.35E+8 N₂ (C³Π_(u)-B³Π_(g))2⁺-system (2-3) 350.05 349.9700 −0.0800 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system(1-2) 353.67 353.6400 −0.0300 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system (0-1)357.69 357.6500 −0.0400 N₂ ⁺ (B²Σ⁺ _(u)-X²⁺ _(g)) 1⁻-system (1-0) 358.2358.2000 0.0000 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system (2-4) 371 370.9500−0.0500 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system (1-3) 375.54 375.4500 −0.0900 N₂(C³Π_(u)-B³Π_(g)) 2⁺-system (0-2) 380.49 380.4000 −0.0900 N₂ ⁺ (B²Σ⁺_(u)-X²⁺ _(g)) 1⁻-system (1-1) 388.4 388.4200 0.0200 N₂ ⁺ (B²Σ⁺ _(u)-X²⁺_(g)) 1⁻-system (0-0) 391.4 391.3700 −0.0300 N₂ (C³Π_(u)-B³Π_(g))2⁺-system (1-4) 399.8 399.7100 −0.0900 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system(0-3) 405.94 405.8600 −0.0800 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system (4-8)409.48 409.4900 0.0100 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system (1-5) 421.2421.1600 −0.0400 N₂ ⁺ (B²Σ⁺ _(u)-X²⁺ _(g)) 1⁻-system (1-2) 424 423.6400−0.3600 N₂ ⁺ (B²Σ⁺ _(u)-X²⁺ _(g)) 1⁻-system (0-1) 427.81 427.8300 0.0200N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system (3-8) 441.67 441.6200 −0.0500 N₂ ⁺ (B²Σ⁺_(u)-X²⁺ _(g)) 1⁻-system (1-3) 465.1 465.1300 0.0300 Ag | 4d¹⁰(¹S) 5p²P⁰ _(3/2) - 4d¹⁰(¹S) 7s ²S_(1/2) 466.8477 466.9100 0.0623 30472.70351886.971 4 2 N₂ ⁺ (B²Σ⁺ _(u)-X²⁺ _(g)) 1⁻-system (0-2) 470.9 470.8400−0.0600 Ag | 4d¹⁰(¹S) 5p ²P⁰ _(1/2) - 4d¹⁰(¹S) 7s ²D_(3/2) 520.9078520.8653 −0.0425 29552.061 48743.969 2 4 7.50E+7 Ag | 4d¹⁰(¹S) 5p ²P⁰_(3/2) - 4d¹⁰(¹S) 5d ²D_(5/2) 546.5497 546.5386 −0.0111 30472.70348764.219 4 6 8.60E+7 Na | 3s ²S_(1/2) - 3p ²P⁰ _(3/2) 588.99 588.9950.0050 H | 2p ²P_(3/2) - 3d ²D_(5/2) 656.2852 655.8447 −0.4405 82259.28797492.357 4 6 6.47E+7 N | 3s ⁴P_(5/2) - 3p ⁴S_(3/2) 746.8312 746.88150.0503 83364.62 96750.84 6 4 1.93E+7 N₂ (B³Π_(g)-A³Σ⁻ _(u)) 1⁺-system750 749.9618 −0.0382 Ag | 4d¹⁰(¹S) 5p ²P⁰ _(1/2) - 4d¹⁰(¹S) 6s ²S_(1/2)768.7772 768.4540 −0.3232 29552.061 42556.152 2 2 O | 3s ⁵S₂-3p⁵P₃777.1944 776.8659 −0.3285 73768.2 86631.454 5 7 3.69E+7 Ag | 4d¹⁰(¹S) 5p²P⁰ _(3/2) - 4d¹⁰(¹S) 6s ²S_(1/2) 827.3509 827.1320 −0.2189 30472.70342556.152 4 2 O | 3s ³S₁ - 3p ³P₂ 844.6359 844.2905 −0.3454 76794.97888631.146 3 5 3.22E+7 N | 3s ⁴P_(5/2) - 3p ⁴D_(7/2) 868.0282 868.22190.1937 83364.62 94881.82 6 8 2.46E+7 O | 3p ⁵P₃ - 3d ⁵D₄ 926.6006926.3226 −0.2780 86631.454 97420.63 7 9 4.45E+7

FIGS. 87A-87D, along with Table 20b, show similar emission spectraassociated with a gold electrode 1 was utilized to create the plasma 4.

TABLE 20b λ meas. λ tab. λ meas. −λ tab. En Em Amn Transition (nm) (nm)(nm) (1/cm) (1/cm) gn gm (1/s) NO A²Σ⁺-X²Π γ-system: (1-0) 214.7214.7000 0.0000 NO A²Σ⁺-X²Π γ-system: (0-0) 226.9 226.8300 −0.0700 NOA²Σ⁺-X²Π γ-system: (0-1) 236.3 236.2100 −0.0900 NO A²Σ⁺-X²Π γ-system:(0-2) 247.1 246.9300 −0.1700 NO A²Σ⁺-X²Π γ-system: (0-3) 258.3 258.53000.2300 Pt | 5d⁹6s ¹D₂ - 5d⁸(¹D)6s6p(3P⁰)³F⁰ ₂ 262.80269 262.8200 0.0173775.892 38815.908 7 5 4.82E+7 Pt | 5d⁹6s ³D₃ - 5d⁹6p³F⁰ ₄ 265.94503265.9000 −0.0450 0 37590.569 7 9 8.90+7 NO A²Σ⁺-X²Π γ-system: (1-1)267.1 267.0600 −0.0400 Pt | 5d⁹6s ¹D₂ - 5d⁹6p³D⁰ ₃ 270.23995 270.2100−0.0300 775.892 37769.073 5 7 5.23E+7 Pt | 5d⁸6s² ³F₄ - 5d⁹6p³D⁰ ₃270.58951 270.5600 −0.0295 823.678 37769.073 9 7 3.80E+7 NO A²Σ⁺-X²Πγ-system: (0-4) 271 271.1400 0.1400 Pt | 5d⁹6s ¹D₂ - 5d⁹6p³P⁰ ₂273.39567 273.3600 −0.0357 775.892 37342.101 5 5 6.72E+7 OH A²Σ-X²Π(1-0) 281.2 281.2000 0.0000 OH A²Σ-X²Π (1-0) 282 281.9600 −0.0400 Pt |5d⁹6s ³D₃ - 5d⁸(³F)6s6p(³P⁰)⁵D⁰ ₃ 283.02919 283.0200 −0.0092 0 35321.6537 7 1.68E+7 Pt | 5d⁹6s ¹D₂ - 5d⁸(³F)6s6p(³P⁰)⁵D⁰ ₃ 289.3863 289.42000.0337 775.892 35321.653 5 7 6.47E+6 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system(4-2) 295.32 295.3300 0.0100 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system (3-1) 296.2296.1900 −0.0100 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system (2-0) 297.7 297.70000.0000 Pt | 5d⁹6s ¹D₂ - 5d⁹6p³F⁰ ₃ 299.79622 299.8600 0.0638 775.89234122.165 5 7 2.88E+7 Pt | 5d⁸6s ³F₄ - 5d⁸(³F)6s6p(³P⁰)⁵F⁰ ₅ 304.26318304.3500 0.0868 823.678 33680.402 9 11 7.69E+6 OH A²Σ-X²Π: (0-0) 306.537306.4600 −0.0770 OH A²Σ-X²Π: (0-0) 306.776 306.8400 0.0640 OH A²Σ-X²Π:(0-0) 307.844 307.8700 0.0260 OH A²Σ-X²Π: (0-0) 308.986 309.0700 0.0840N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system (2-1) 313.57 313.5800 0.0100 N₂(C³Π_(u)-B³Π_(g)) 2⁺-system (1-0) 316 315.9200 −0.0800 O₂ (B³Σ⁻_(u)-X³Σ⁻ _(g)) (0-14) 337 337.0800 0.0800 N₂ (C³Π_(u)-B³Π_(g))2⁺-system (0-0) 337.1 337.1400 0.0400 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system(2-3) 350.05 349.9700 −0.0800 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system (1-2)353.67 353.6400 −0.0300 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system (0-1) 357.69357.6500 −0.0400 N₂ ⁺ (B³Σ⁺ _(u)-X²⁺ _(g)) 1⁻-system (1-0) 358.2358.2000 0.0000 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system (2-4) 371 370.9500−0.0500 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system (1-3) 375.54 375.4500 −0.0900 N₂(C³Π_(u)-B³Π_(g)) 2⁺-system (0-2) 380.49 380.4000 −0.0900 N₂ ⁺ (B²Σ⁺_(u)-X²⁺ _(g)) 1⁻-system (1-1) 388.4 388.4200 0.0200 N₂ ⁺ (B²Σ⁺ _(u)-X²⁺_(g)) 1⁻-system (0-0) 391.4 391.3700 −0.0300 N₂ (C³Π_(u)-B³Π_(g))2⁺-system (1-4) 399.8 399.7100 −0.0900 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system(0-3) 405.94 405.8100 −0.1300 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system (4-8)409.48 409.4900 0.0100 N₂ ⁺ (B²Σ⁺ _(u)-X²⁺ _(g)) 1⁻-system (2-3) 419.96420.0000 0.0400 N₂ ⁺ (B²Σ⁺ _(u)-X²⁺ _(g)) 1⁻-system (1-2) 423.65423.6400 −0.0100 N₂ ⁺ (B²Σ⁺ _(u)-X²⁺ _(g)) 1⁻-system (0-1) 427.785427.7700 −0.0150 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system (3-8) 441.67 441.6200−0.0500 N₂ ⁺ (B²Σ⁺ _(u)-X²⁺ _(g)) 1⁻-system (1-3) 465.1 465.1300 0.0300N₂ ⁺ (B²Σ⁺ _(u)-X²⁺ _(g)) 1⁻-system (0-2) 470.9 470.8400 −0.0600 Na | 3s²S_(1/2) - 3p ²P⁰ _(3/2) 588.99 588.995 0.0050 H | 2p ²P_(3/2) - 3d²D_(5/2) 656.2852 655.8447 −0.4405 82259.287 97492.357 4 6 6.47E+07 N |3s ⁴P_(5/2) - 3p ⁴S_(3/2) 746.8312 746.8815 0.0503 83364.62 96750.84 6 41.93E+07 N₂ (B³Π_(g) - A³Σ⁻ _(u)) 1⁺-system 750 749.9618 −0.0382 O | 3s⁵S₂-3p⁵P₃ 777.1944 776.8659 −0.3285 73768.2 86631.454 5 7 3.69E+07 O |3s ³S₁ - 3p ³P₂ 844.6359 844.2905 −0.3454 76794.978 88631.146 3 53.22E+07 N | 3s ⁴P_(5/2) - 3p ⁴D_(7/2) 868.0282 868.2219 0.1937 83364.6294881.82 6 8 2.46E+07 O | 3p ⁵P₃ - 3d ⁵D₄ 926.6006 926.3226 −0.278086631.454 97420.63 7 9 4.45E+07

FIGS. 88A-88D, along with Table 20c, show similar emission spectraassociated with a platinum electrode 1 was utilized to create the plasma4.

TABLE 20c λ meas. λ tab. λ meas. −λ tab. En Em Amn Transition (nm) (nm)(nm) (1/cm) (1/cm) gn gm (1/s) NO A²Σ⁺-X²Π γ-system: (1-0) 214.7214.7000 0.0000 NO A²Σ⁺-X²Π γ-system: (0-0) 226.9 226.8300 −0.0700 NOA²Σ⁺-X²Π γ-system: (0-1) 236.3 236.2100 −0.0900 Au | 5d¹⁰6s ²S_(1/2) -5d¹⁰6p ²P⁰ _(3/2) 242.795 242.7900 −0.0050 0 41174.613 2 4 1.99E+8 NOA²Σ⁺-X²Π γ-system: (0-2) 247.1 246.9300 −0.1700 NO A²Σ⁺-X²Π γ-system:(0-3) 258.3 258.5300 0.2300 NO A²Σ⁺-X²Π γ-system: (1-1) 267.1 267.0600−0.0400 Au | 5d¹⁰6s ²S_(1/2) - 5d¹⁰6p ²P⁰ _(1/2) 267.595 267.59 −0.00500 37358.991 2 2 1.64E+8 NO A²Σ⁺-X²Π γ-system: (0-4) 271 271.1400 0.1400Au | 5d⁹6s² ²D_(5/2) - 5d⁹(²D_(5/2))6s6p ²4⁰ _(7/2) 274.825 274.82−0.0050 9161.177 45537.195 6 8 OH A²Σ-X²Π (1-0) 281.2 281.2000 0.0000 OHA²Σ-X²Π (1-0) 282 281.9600 −0.0400 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system (4-2)295.32 295.3300 0.0100 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system (3-1) 296.2296.1900 −0.0100 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system (2-0) 297.7 297.70000.0000 OH A²Σ-X²Π: (0-0) 306.537 306.4600 −0.0770 OH A²Σ-X²Π: (0-0)306.776 306.8400 0.0640 OH A²Σ-X²Π: (0-0) 307.844 307.8700 0.0260 OHA²Σ-X²Π: (0-0) 308.986 309.0700 0.0840 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system(2-1) 313.57 313.5800 0.0100 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system (1-0) 316315.9200 −0.0800 O₂ (B³Σ⁻ _(u)-X³Σ⁻ _(g)) (0-14) 337 337.0800 0.0800 N₂(C³Π_(u)-B³Π_(g)) 2⁺-system (0-0) 337.1 337.1400 0.0400 N₂(C³Π_(u)-B³Π_(g)) 2⁺-system (2-3) 350.05 349.9700 −0.0800 N₂(C³Π_(u)-B³Π_(g)) 2⁺-system (1-2) 353.67 353.6400 −0.0300 N₂(C³Π_(u)-B³Π_(g)) 2⁺-system (0-1) 357.69 357.6500 −0.0400 N₂ ⁺ (B²Σ⁺_(u)-X²⁺ _(g)) 1⁻-system (1-0) 358.2 358.2000 0.0000 N₂(C³Π_(u)-B³Π_(g)) 2⁺-system (2-4) 371 370.9500 −0.0500 N₂(C³Π_(u)-B³Π_(g)) 2⁺-system (1-3) 375.54 375.4500 −0.0900 N₂(C³Π_(u)-B³Π_(g)) 2⁺-system (0-2) 380.49 380.4000 −0.0900 N₂ ⁺ (B²Σ⁺_(u)-X²⁺ _(g)) 1⁻-system (1-1) 388.4 388.4200 0.0200 N₂ ⁺ (B²Σ⁺ _(u)-X²⁺_(g)) 1⁻-system (0-0) 391.4 391.3700 −0.0300 N₂ (C³Π_(u)-B³Π_(g))2⁺-system (1-4) 399.8 399.7100 −0.0900 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system(0-3) 405.94 405.8100 −0.1300 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system (4-8)409.48 409.4900 0.0100 N₂ ⁺ (B²Σ⁺ _(u)-X²⁺ _(g)) 1⁻-system (2-3) 419.96420.0000 0.0400 N₂ ⁺ (B²Σ⁺ _(u)-X²⁺ _(g)) 1⁻-system (1-2) 423.65423.6400 −0.0100 N₂ ⁺ (B²Σ⁺ _(u)-X²⁺ _(g)) 1⁻-system (0-1) 427.785427.7700 −0.0150 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system (3-8) 441.67 441.6200−0.0500 Au | 5d⁹(²D_(5/2))6s6p ²4⁰ _(7/2) - 5d⁹(²D_(5/2))6s7s 10_(7/2)448.8263 448.7500 −0.0763 45537.195 67811.329 8 8 N₂ ⁺ (B²Σ⁺ _(u)-X²⁺_(g)) 1⁻-system (1-3) 465.1 465.1300 0.0300 N₂ ⁺ (B²Σ⁺ _(u)-X²⁺ _(g))1⁻-system (0-2) 470.9 470.8400 −0.0600 Na | 3s ²S_(1/2) - 3p ²P⁰ _(3/2)588.99 588.995 0.0050 H | 2p ²P_(3/2) - 3d ²D_(5/2) 656.2852 655.8447−0.4405 82259.287 97492.357 4 6 6.47E+7 N | 3s ⁴P_(5/2) - 3p ⁴S_(3/2)746.8312 746.8815 0.0503 83364.62 96750.84 6 4 1.93E+7 N₂ (B³Π_(g) -A³Σ⁻ _(u)) 1⁺-system 750 749.9618 −0.0382 O | 3s ⁵S₂-3p⁵P₃ 777.1944776.8659 −0.3285 73768.2 86631.454 5 7 3.69E+7 O | 3s ³S₁ - 3p ³P₂844.6359 844.2905 −0.3454 76794.978 88631.146 3 5 3.22E+7 N | 3s⁴P_(5/2) - 3p ⁴D_(7/2) 868.0282 868.2219 0.1937 83364.62 94881.82 6 82.46E+7 O | 3p ⁵P₃ - 3d ⁵D₄ 926.6006 926.3226 −0.2780 86631.454 97420.637 9 4.45E+7

FIG. 88E, along with Table 20d, show the emission spectra associatedwith a platinum electrode 1 utilized to create the plasma 4. Adifference between the spectra shown in FIGS. 88D and 88E is apparent.The primary reason for the differences noted is that the power sourcetransformer 10 shown in FIG. 85 has been increased from about 60 mA toabout 120 mA by electrically connecting two transformers (discussedabove herein) together in parallel. The voltage output from the twotransformers 10 was about 800-3,000 volts, in comparison to about900-2,500 volts when a single transformer was used. Many more “Pt” peaksbecome apparent. Table 20d sets forth all of the species identified whentwo transformers 10 are utilized.

TABLE 20d λ meas. λ tab. λ meas. −λ tab. En Em Amn Transition (nm) (nm)(nm) (1/cm) (1/cm) gn gm (1/s) NO A²Σ⁺-X²Π γ-system: (1-0) 214.7214.7000 0.0000 Pt | 217.46853 217.5100 0.0415 NO A²Σ⁺-X²Π γ-system:(0-0) 226.9 226.8300 −0.0700 NO A²Σ⁺-X²Π γ-system: (1-0) 236.3 236.2100−0.0900 Pt | 242.804 242.8500 0.0460 Pt | 244.00608 244.0000 −0.0061 NOA²Σ⁺-X²Π γ-system: (0-2) 247.1 246.9300 −0.1700 Pt | 5d⁹6s ¹D₂ -5d⁸(³F)6s6p(3P⁰)⁵G⁰ ₃ 248.71685 248.7100 −0.0068 775.892 40970.165 5 7Pt | 251.5577 251.5900 0.0323 NO A²Σ⁺-X²Π γ-system: (0-3) 258.3 258.53000.2300 Pt | 5d⁹6s ¹D₂ - 5d⁸(¹D)6s6p(3P⁰)³F⁰ ₂ 262.80269 262.8200 0.0173775.892 38815.908 7 5 4.82E+7 Pt | 264.68804 264.6200 −0.0680 Pt | 5d⁹6s³D₃ - 5d⁹6p³F⁰ ₄ 265.94503 265.9000 −0.0450 0 37590.569 7 9 8.90E+7 NOA²Σ⁺-X²Π γ-system: (1-1) 267.1 267.0600 −0.0400 Pt | 267.71477 267.6500−0.0648 Pt | 5d⁹6s ¹D₂ - 5d⁹6p³D⁰ ₃ 270.23995 270.2100 −0.0300 775.89237769.073 5 7 5.23E+7 Pt | 5d⁸6s² ³F₄ - 5d⁹6p³D⁰ ₃ 270.58951 270.5600−0.0295 823.678 37769.073 9 7 3.80E+7 NO A²Σ⁺-X²Π γ-system: (0-4) 271271.1400 0.1400 Pt | 271.90333 271.9000 −0.0033 Pt || 5d⁸(³F₃)6p_(1/2)(3, 1/2)⁰ - 5d⁸(¹D)7s ²D_(3/2) 271.95239 271.9000 −0.0524 64757.343101517.59 6 4 Pt | 5d⁹6s ¹D₂ - 5d⁹6p³P⁰ ₂ 273.39567 273.3600 −0.0357775.892 37342.101 5 5 6.72E+7 Pt | 275.38531 275.4600 0.0747 Pt |277.16594 277.2200 0.0541 OH A²Σ-X²Π (1-0) 281.2 281.2600 0.0600 OHA²Σ-X²Π (1-0) 282 281.9600 −0.0400 Pt | 5d⁹6s ³D₃ - 5d⁸(³F)6s6p(³P⁰)⁵D⁰₃ 283.02919 283.0200 −0.0092 0 35321.653 7 7 1.68E+7 Pt | 5d⁹6s ¹D₂ -5d⁸(³F)6s6p(³P⁰)⁵D⁰ ₃ 289.3863 289.4200 0.0337 775.892 35321.653 5 76.47E+6 Pt | 5d⁹6s ³D₃ - 5d⁹6p³F⁰ ₃ 292.97894 293.0700 0.0911 034122.165 7 7 1.85E+7 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system (4-2) 295.32295.3300 0.0100 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system (3-1) 296.2 296.1900−0.0100 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system (2-0) 297.7 297.7000 0.0000 Pt |5d⁹6s ¹D₂ - 5d⁹6p³F⁰ ₃ 299.79622 299.8600 0.0638 775.892 34122.165 5 72.88E+7 Pt | 5d⁸6s² ³F₄ - 5d⁸(³F)6s6p(³P⁰)⁵F⁰ ₅ 304.26318 304.35000.0868 823.678 33680.402 9 11 7.69E+6 OH A²Σ-X²Π: (0-0) 306.537 306.4600−0.0770 OH A²Σ-X²Π: (0-0) 306.776 306.8400 0.0640 OH A²Σ-X²Π: (0-0)307.844 307.8700 0.0260 OH A²Σ-X²Π: (0-0) 308.986 309.0700 0.0840 N₂(C³Π_(u)-B³Π_(g)) 2⁺-system (2-1) 313.57 313.5800 0.0100 N₂(C³Π_(u)-B³Π_(g)) 2⁺-system (1-0) 316 315.9200 −0.0800 O₂ (B³Σ⁻_(u)-X³Σ⁻ _(g)) (0-14) 337 337.0800 0.0800 N₂ (C³Π_(u)-B³Π_(g))2⁺-system (0-0) 337.1 337.1400 0.0400 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system(2-3) 350.05 349.9700 −0.0800 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system (1-2)353.67 353.6400 −0.0300 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system (0-1) 357.69357.6500 −0.0400 N₂ ⁺ (B²Σ⁺ _(u)-X²⁺ _(g)) 1⁻-system (1-0) 358.2358.2000 0.0000 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system (2-4) 371 370.9500−0.0500 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system (1-3) 375.54 375.4500 −0.0900 N₂(C³Π_(u)-B³Π_(g)) 2⁺-system (0-2) 380.49 380.4000 −0.0900 N₂ ⁺ (B²Σ⁺_(u)-X²⁺ _(g)) 1⁻-system (1-1) 388.4 388.4200 0.0200 N₂ ⁺ (B²Σ⁺ _(u)-X²⁺_(g)) 1⁻-system (0-0) 391.4 391.3700 −0.0300 N₂ (C³Π_(u)-B³Π_(g))2⁺-system (1-4) 399.8 399.7100 −0.0900 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system(0-3) 405.94 405.8100 −0.1300 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system (4-8)409.48 409.4900 0.0100 N₂ ⁺ (B²Σ⁺ _(u)-X²⁺ _(g)) 1⁻-system (2-3) 419.96420.0000 0.0400 N₂ ⁺ (B²Σ⁺ _(u)-X²⁺ _(g)) 1⁻-system (1-2) 423.65423.6400 −0.0100 N₂ ⁺ (B²Σ⁺ _(u)-X²⁺ _(g)) 1⁻-system (0-1) 427.785427.7700 −0.0150 N₂ (C³Π_(u)-B³Π_(g)) 2⁺-system (3-8) 441.67 441.6200−0.0500 N₂ ⁺ (B²Σ⁺ _(u)-X²⁺ _(g)) 1⁻-system (1-3) 465.1 465.1300 0.0300N₂ ⁺ (B²Σ⁺ _(u)-X²⁺ _(g)) 1⁻-system (0-2) 470.9 470.8400 −0.0600 Na | 3s²S_(1/2) - 3p ²P⁰ _(3/2) 588.99 588.995 0.0050 H | 2p ²P_(3/2) - 3d²D_(5/2) 656.2852 655.8447 −0.4405 82259.287 97492.357 4 6 6.47E+7 N |3s ⁴P_(5/2) - 3p ⁴S_(3/2) 746.8312 746.8815 0.0503 83364.62 96750.84 6 41.93E+7 N₂ (B³Π_(g) - A³Σ⁻ _(u)) 1⁺-system 750 749.9618 −0.0382 O | 3s⁵S₂-3p⁵P₃ 777.1944 776.8659 −0.3285 73768.2 86631.454 5 7 3.69E+7 O | 3s³S₁ - 3p ³P₂ 844.6359 844.2905 −0.3454 76794.978 88631.146 3 5 3.22E+7 N| 3s ⁴P_(5/2) - 3p ⁴D_(7/2) 868.0282 868.2219 0.1937 83364.62 94881.82 68 2.46E+7 O | 3p ⁵P₃ - 3d ⁵D₄ 926.6006 926.3226 −0.2780 86631.45497420.63 7 9 4.45E+7

A variety of similar species associated with each metallic electrodecomposition plasma are identified in Tables 20a-20d. These speciesinclude, for example, the various metal(s) from the electrodes 1, aswell as common species including, NO, OH, N₂, etc. It is interesting tonote that some species' existence and/or intensity (e.g., amount) is afunction of location within the adjustable plasma. Accordingly, thissuggests that various species can be caused to occur as a function of avariety of processing conditions (e.g., power, location, composition ofelectrode 1, etc.) of the invention.

FIGS. 89A-89D show additional information derived from the apparatusshown in FIG. 85. FIG. 89A notes three different peak heights “G₀”, “G₁”and G_(ref)”. These spectra come from a portion of FIG. 86B (i.e., thatportion between d=305 and d=310). Generally, the ratio of the height ofthese peaks can be used to determine the temperature of the adjustableplasma 4. The molecular OH temperatures (FIG. 89B) for a plasma 4created by a silver electrode discharging in air above water, weremeasured from the spectral line ratios G₀/G_(Ref) and G₁/G_(Ref)originating from A²S-X²P transitions in OH (FIG. 89A) for theinstrumental line broadening of 0.13 nm at 313.3 nm, following theprocedures described in Reference 2, expressly incorporated by referenceherein.

Moreover, the plasma electron temperatures (see FIG. 89B) for a plasma 4created by a silver electrode 1 discharging in air above water, weremeasured from the Boltzmann plot (see Reference 1), expresslyincorporated by reference herein] of the “Ag I” line intensitiesoriginating from two spectral doublets:

AgI4d ¹⁰(¹S)5s ²S_(1/2)-4d ¹⁰(¹S)5p ²P⁰ _(3/2)

AgI4d ¹⁰(¹S)5s ²S_(1/2)-4d ¹⁰(¹S)5p ²P⁰ _(1/2)

AgI4d ¹⁰(¹S)5p ²P⁰ _(1/2)-4d ¹⁰(¹S)5d ²D_(3/2)

AgI4d ¹⁰(¹S)5p ²P⁰ _(3/2)-4d ¹⁰(¹S)5d ²D_(5/2)

Spectral line intensities used in all temperature measurements are givenin units of spectral irradiance (mW/m²/nm) after the irradiancecalibration of the spectrometers was performed.

FIG. 89B plots the plasma temperature, as a function of position awayfrom the tip 9 of the electrode 1, when a silver electrode is present.

FIGS. 89C and 89D show the integrated intensities of “NO” and “OH” as afunction of position and electrode 1 composition. Note that in FIG. 89C,the lines from “Ag” and “Au” overlap substantially.

REFERENCES

-   [1] Hans R. Griem, Principles of Plasma Spectroscopy, Cambridge    Univ. Press (1996).-   [2] Charles de Izarra, J. Phys. D: Appl. Phys. 33 (2000) 1697-1704.

Example 17 Comparison of Zeta Potential of Silver-BasedNanoparticles/Nanoparticle Solutions by Adding Variable ZincNanoparticles/Nanoparticle Solutions

The materials disclosed in Examples 11 and 12, namely, AT-060 and BT-06,were mixed together in varying proportions to form several differentsolutions to determine if any differences in zeta potential could beobserved as a function of volumetric proportions in the variousmixtures.

In this Example, a Zeta-Sizer “Nano-ZS” produced by Malvern Instrumentswas utilized to determine the zeta potential of each solution. For eachmeasurement, a 1 ml sample was filled into clear disposable zeta cellDTS1060C. Dispersion Technology Software, version 5.10 was used to runthe Zeta-Sizer and to calculate the zeta potential. The followingsettings were used: dispersant—water, temperature—25° C.,viscosity—0.8872 cP, refraction index—1.330, dielectric constant—78.5,approximation model—Smoluchowski. One run of hundred repetitions wasperformed for each sample.

“Zeta potential” is known as a measure of the electo-kinetic potentialin colloidal systems. Zeta potential is also referred to as surfacecharge on particles. Zeta potential is also known as the potentialdifference that exists between the stationary layer of fluid and thefluid within which the particle is dispersed. A zeta potential is oftenmeasured in millivolts (i.e., mV). The zeta potential value ofapproximately 25 mV is an arbitrary value that has been chosen todetermine whether or not stability exists between a dispersed particlein a dispersion medium. Thus, when reference is made herein to “zetapotential”, it should be understood that the zeta potential referred tois a description or quantification of the magnitude of the electricalcharge present at the double layer.

The zeta potential is calculated from the electrophoretic mobility bythe Henry equation:

$U_{E} = \frac{2ɛ\; {{zf}({ka})}}{3\eta}$

where z is the zeta potential, U_(E) is the electrophoretic mobility, ∈is a dielectric constant, η is a viscosity, ƒ(ka) is Henry's function.For Smoluchowski approximation ƒ(ka)=1.5.

Electrophoretic mobility is obtained by measuring the velocity of theparticles in applied electric field using Laser Doppler Velocimetry(LDV). In LDV the incident laser beam is focused on a particlesuspension inside a folded capillary cell and the light scattered fromthe particles is combined with the reference beam. This produces afluctuating intensity signal where the rate of fluctuation isproportional to the speed of the particles, i.e. electrophoreticmobility.

As Table 21a below indicates, AT-060, BT-06 and DI water were mixed indifferent proportions and the zeta potential was measured right aftermixing and one day after mixing. The results for zeta potential areshown in the table below. A clear trend exists for zeta potential ofAg:Zn 4:0 (−28.9) to Ag:Zn 0:4 (+22.7).

TABLE 21a Composition of Sample Concentration (ml) (ppm) Zeta Potential(mV) Sample ID AT060 BT06 DI Water Ag Zn Freshly Mixed After One DayAg:Zn 4:0 2 0 2 20 0 −28.9 n/a Ag:Zn 4:1 2 0.5 1.5 20 3 −16.7 −22.5Ag:Zn 4:2 2 1 1 20 6 −13.9 −18.1 Ag:Zn 4:3 2 1.5 0.5 20 9 −12.4 −11.4Ag:Zn 4:4 2 2 0 20 12 −12.4 −10.3 Ag:Zn 0:4 0 2 2 0 12 +22.7 n/a

As a comparison, zinc sulfate heptahydrate (ZnSO₄7H₂O) having a formulaweight of 287.58 was added in varying quantities to the AT-060 solutionto determine if a similar trend in zeta potential change could beobserved for different amounts of zinc sulfate being added. The zincsulfate heptahydrate was obtained from Fisher Scientific, had a Product# of Z68-500, a Cas # of 7446-20-0 and a Lot # of 082764. After mixing,the zeta potential of the AT-060/ZnSO₄7H₂O mixture was measured. Thedata were very mixed and no clear trends in changes in zeta potentialwere evident.

Example 18 Biological Efficacy of Various Solutions Against Bacteria andFungi

The biological efficacy of seven different solutions made according tothe inventive teachings herein, were tested for efficacy against avariety of bacteria and fungi.

The biological efficacy measurements made in Example 18 are differentfrom those discussed earlier herein (e.g., the biologicalcharacterization discussed relative to Examples 1-5). Specifically,MIC/MID 50 levels were determined for each of the seven differentsolutions. The clinical and laboratory standards institute BrothMicrodilution Methodology was employed, however, the growth medium usedwas an “RPMI” medium.

Additionally, the methods for dilution and antimicrobial susceptibilitytests for bacteria that grow aerobically were also followed with thenoted exception of testing with alternative media (CLSI document M7A7,CLSI, Wayne, Pa.).

The seven different solutions tested for efficacy were GR-05, GR-08,GR-21, GR-01, GR-24, GR-25 and GR-26. The solutions GR-05, GR-08 andGR-01 were previously discussed herein in conjunction with Examples 1-5.The solutions GR-24, GR-25 and GR-26 correspond to different mixtures ofthe same components used to form GR-05. In this regard, the volumetricproportions of GR-24 were 40% Ag/60% Zn; the volumetric proportions forGR-25 were 50% Ag/50% Zn; and the volumetric proportions for GR-26 were60% Ag/40% Zn. Solution GR-21 corresponded to GR-08 for its Ag solution,but the Zn solution was replaced with an equivalent amount of solutionPT001 made in accordance with the teachings in Example 11.

Table 22a shows results of the seven different solutions against avariety of bacteria. Under the column, “Isolate” identificationbeginning with either “GP” or “GN” occur. The “GP” corresponds toGram-Positive bacteria and the “GN” corresponds to “Gram Negative”bacteria. Each of the organisms are specifically listed after theisolate identification. Table 22b shows the same testing results, butreported in a different way.

TABLE 22a

TABLE 22b ug/ml ug/ml ug/ml ug/ml ug/ml ug/ml ug/ml Organism GR-21 GR-08GR-05 GR-01 GR-24 GR-25 GR-26 Citrobacter freundii -antibiotic-susceptible clinical isolate 0.21 0.23 0.16 0.20 0.23 0.020.02 Stenotrophomonas maltophilia - antibiotic-susceptible clinicalisolate 0.05 0.06 0.04 0.05 0.06 0.04 0.08 Acinetobacter baumanii -multi-drug resistant clinical isolate 0.11 0.12 0.08 0.10 0.12 0.07 0.08Burkholderia cepacia - antibiotic-susceptible clinical isolate 0.11 0.120.16 0.10 0.12 0.07 0.17 Pseudomonas aeruginosa - multi-drug resistantclinical isolate 0.11 0.12 0.08 0.10 0.12 0.07 0.08 Stenotrophomonasmaltophila - antibiotic-resistant clinical isolate 0.11 0.12 0.16 0.100.12 0.07 0.17 Acinetobacter baumanii - antibiotic-susceptible clinicalisolate 0.11 0.12 0.08 0.10 0.12 0.07 0.17 Moraxella catarrhalisβ-lactamase positive clinical isolate 0.11 0.12 0.16 0.10 0.06 0.07 0.17Moraxella catarrhalis β-lactamase positive clinical isolate 0.11 0.120.16 0.10 0.12 0.07 0.17 Shigella sp - multi-drug resistant clinicalisolate 0.11 0.12 0.08 0.10 0.12 0.07 0.17 Enterococcus faeciumvancomycin-resistant (VanB) clinical isolate 0.11 0.12 0.16 0.10 0.120.14 0.08 Listeria monocytogenes - antibiotic-susceptible clinicalisolate 0.21 0.23 0.33 0.20 0.23 0.14 0.33 Citrobacter freundii -resistant clinical isolate 0.21 0.46 0.33 0.20 0.23 0.14 0.17Providencia stuartii - multi-drug resistant clinical isolate 0.21 0.230.16 0.20 0.23 0.14 0.33 Staphylococcus aureus - multi-drug-resistantclinical isolate 0.21 0.23 0.16 0.20 0.23 0.14 0.17 Staphylococcusaureus - teicoplanin-intermediate clinical isolate 0.21 0.23 0.33 0.200.23 0.14 0.17 Enterococcus faecalis - ATCC 29212 antibiotic-susceptiblecontrol strain 0.21 0.23 0.33 0.20 0.23 0.14 0.33 Pseudomonas aeruginosaATCC27853 - antibiotic-susceptible type strain 0.11 0.12 0.16 0.20 0.120.14 0.17 Streptococcus bovis - antibiotic-susceptible clinical isolate0.21 0.23 0.33 0.20 0.23 0.14 0.17 Streptococcus bovis -macrolide-resistant clinical isolate 0.21 0.23 0.16 0.20 0.23 0.14 0.17Staphylococcus haemolyticus - antibiotic susceptible clinical isolate0.11 0.12 0.16 0.20 0.12 0.14 0.17 Staphylococcus saprophyticus -antibiotic susceptible clinical isolate 0.21 0.23 0.16 0.20 0.23 0.140.33 Staphylococcus aureus ATCC 43300 - methicillin-resistant controlstrain 0.11 0.23 0.16 0.20 0.23 0.14 0.17 Staphylococcus epidermidismethicillin-resistant clinical isolate 0.11 0.23 0.16 0.20 0.12 0.140.17 Staphylococcus aureus - methicillin-resistant clinical isolate 0.210.23 0.16 0.20 0.12 0.14 0.17 Staphylococcus aureus ATCC 25923 -antibiotic-susceptible control strain 0.11 0.12 0.16 0.20 0.12 0.14 0.17Staphylococcus aureus ATCC 29213 - antibiotic-susceptible control strain0.21 0.23 0.16 0.20 0.23 0.14 0.17 Staphylococcus epidermidis antibioticsusceptible clinical isolate 0.21 0.23 0.16 0.20 0.23 0.14 0.17Providencia stuartii - antibiotic-susceptible clinical isolate 0.21 0.230.33 0.20 0.12 0.14 0.33 Shigella sp - antibiotic-susceptible clinicalisolate 0.11 0.12 0.16 0.10 0.12 0.14 0.17 Streptococcus pyogenes -Macrolide (MLS) resistant clinical isolate 0.43 0.46 0.33 0.40 0.23 0.280.33 Enterococcus faecalis vancomycin-susceptible clinical isolate 0.210.23 0.33 0.20 0.23 0.28 0.33 Morganella morganii - multi-drug resistantclinical isolate 0.43 0.46 0.16 0.40 0.12 0.28 0.66 Streptococcusagalactiae - antibiotic-susceptible clinical isolate 0.85 0.91 1.31 0.400.47 0.28 0.33 Streptococcus agalactiae - macrolide-resistant clinicalisolate 0.21 0.91 1.31 0.40 0.23 0.28 0.33 Streptococcus mitis -macrolide-resistant clinical isolate 0.43 0.46 0.33 0.40 0.47 0.28 0.33Streptococcus pneumoniae - multi-drug resistant clinical isolate 0.430.46 0.33 0.40 0.23 0.28 0.33 Streptococcus pneumoniae - ATCC 49619antibiotic-susceptible control strain 0.43 0.46 0.33 0.40 0.47 0.28 0.33Streptococcus pneumoniae - pencillin-susceptible clinical isolate 0.430.46 0.33 0.40 0.47 0.28 0.33 Streptococcus sanguis -macrolide-resistant clinical isolate 0.43 0.23 0.33 0.20 0.23 0.28 0.33Streptococcus pneumoniae - penicillin-intermediate clinical isolate 0.210.46 0.33 0.40 0.47 0.28 0.33 Streptococcus pneumoniae -penicillin-resistant clinical isolate 0.43 0.23 0.33 0.40 0.47 0.28 0.33Streptococcus sanguis - antibiotic-susceptible clinical isolate 0.430.23 0.33 0.40 0.47 0.28 0.33 Enterobacter sp - multi-drug resistantclinical isolate 0.43 0.46 0.33 0.78 0.23 0.28 0.33 Proteus mirabilis -antibiotic-susceptible clinical isolate 0.43 0.23 0.16 0.20 0.23 0.280.33 Salmonella sp - multi-drug resistant clinical isolate 0.21 0.230.16 0.20 0.23 0.28 0.66 Klebsiella aerogenes NCTC11228 -antibiotic-susceptible type strain 0.85 0.46 0.33 0.40 0.47 0.28 0.33Escherichia coli ATCC25922 - antibiotic-susceptible type strain 0.210.12 0.16 0.20 0.23 0.28 0.17 Serratia marcescens - multi-drug resistantclinical isolate 0.21 0.46 0.33 0.20 0.23 0.56 0.66 Enterococcusgallinarum vancomycin-resistant (VanC) clinical isolate 0.43 0.46 0.660.40 0.47 0.56 0.66 Proteus mirabilis - multi-drug resistant clinicalisolate 0.85 0.46 0.33 0.78 0.93 0.56 1.33 Klebsiella aerogenes -multi-drug resistant clinical isolate 0.85 0.46 0.16 0.78 0.93 0.56 1.33Streptococcus oralis - antibiotic-susceptible clinical isolate 0.43 0.460.66 0.40 0.47 0.56 0.66 Streptococcus oralis - macrolide-resistantclinical isolate 0.43 0.46 0.66 0.78 0.47 0.56 0.66 Enterobacter sp -antibiotic-susceptible clinical isolate 1.70 0.46 0.66 0.78 0.93 0.561.33 Serratia marcescens - antibiotic-susceptible clinical isolate 0.430.23 0.33 0.40 0.47 0.56 0.66 ug/ml Relative Efficacy Levels OrganismLevofloxacin LVF/GR-25 LVF/GR-8 LVF/GR-5 Citrobacter freundii -antibiotic-susceptible clinical isolate 0.02 0.9 0.1 0.1Stenotrophomonas maltophilia - antibiotic-susceptible clinical isolate0.25 7.1 4.2 6.3 Acinetobacter baumanii - multi-drug resistant clinicalisolate 8.00 113.8 66.7 100.0 Burkholderia cepacia -antibiotic-susceptible clinical isolate 4.00 56.9 33.3 25.0 Pseudomonasaeruginosa - multi-drug resistant clinical isolate 2.00 28.4 16.7 25.0Stenotrophomonas maltophila - antibiotic-resistant clinical isolate 1.0014.2 8.3 6.3 Acinetobacter baumanii - antibiotic-susceptible clinicalisolate 0.12 1.7 1.0 1.5 Moraxella catarrhalis β-lactamase positiveclinical isolate 0.06 0.9 0.5 0.4 Moraxella catarrhalis β-lactamasepositive clinical isolate 0.06 0.9 0.5 0.4 Shigella sp - multi-drugresistant clinical isolate 0.03 0.4 0.3 0.4 Enterococcus faeciumvancomycin-resistant (VanB) clinical isolate 4.00 28.6 33.3 25.0Listeria monocytogenes - antibiotic-susceptible clinical isolate 0.503.6 2.2 1.5 Citrobacter freundii - resistant clinical isolate 8.00 56.917.4 24.2 Providencia stuartii - multi-drug resistant clinical isolate8.00 56.9 34.8 50.0 Staphylococcus aureus - multi-drug-resistantclinical isolate 4.00 28.4 17.4 25.0 Staphylococcus aureus -teicoplanin-intermediate clinical isolate 4.00 28.4 17.4 12.1Enterococcus faecalis - ATCC 29212 antibiotic-susceptible control strain2.00 14.2 8.7 6.1 Pseudomonas aeruginosa ATCC27853 -antibiotic-susceptible type strain 1.00 7.1 8.3 6.3 Streptococcusbovis - antibiotic-susceptible clinical isolate 1.00 7.1 4.3 3.0Streptococcus bovis - macrolide-resistant clinical isolate 1.00 7.1 4.36.3 Staphylococcus haemolyticus - antibiotic susceptible clinicalisolate 0.50 3.6 4.2 3.1 Staphylococcus saprophyticus - antibioticsusceptible clinical isolate 0.50 3.6 2.2 3.1 Staphylococcus aureus ATCC43300 - methicillin-resistant control strain 0.25 1.8 1.1 1.6Staphylococcus epidermidis methicillin-resistant clinical isolate 0.251.8 1.1 1.6 Staphylococcus aureus - methicillin-resistant clinicalisolate 0.12 0.9 0.5 0.8 Staphylococcus aureus ATCC 25923 -antibiotic-susceptible control strain 0.12 0.9 1.0 0.8 Staphylococcusaureus ATCC 29213 - antibiotic-susceptible control strain 0.12 0.9 0.50.8 Staphylococcus epidermidis antibiotic susceptible clinical isolate0.12 0.9 0.5 0.8 Providencia stuartii - antibiotic-susceptible clinicalisolate 0.06 0.4 0.3 0.2 Shigella sp - antibiotic-susceptible clinicalisolate 0.03 0.2 0.3 0.2 Streptococcus pyogenes - Macrolide (MLS)resistant clinical isolate 0.50 1.8 1.1 1.5 Enterococcus faecalisvancomycin-susceptible clinical isolate 4.00 14.2 17.4 12.1 Morganellamorganii - multi-drug resistant clinical isolate 1.00 3.6 2.2 6.3Streptococcus agalactiae - antibiotic-susceptible clinical isolate 1.003.6 1.1 0.8 Streptococcus agalactiae - macrolide-resistant clinicalisolate 1.00 3.6 1.1 0.8 Streptococcus mitis - macrolide-resistantclinical isolate 1.00 3.6 2.2 3.0 Streptococcus pneumoniae - multi-drugresistant clinical isolate 1.00 3.6 2.2 3.0 Streptococcus pneumoniae -ATCC 49619 antibiotic-susceptible control strain 1.00 3.6 2.2 3.0Streptococcus pneumoniae - pencillin-susceptible clinical isolate 1.003.6 2.2 3.0 Streptococcus sanguis - macrolide-resistant clinical isolate1.00 3.6 4.3 3.0 Streptococcus pneumoniae - penicillin-intermediateclinical isolate 0.50 1.8 1.1 1.5 Streptococcus pneumoniae -penicillin-resistant clinical isolate 0.50 1.8 2.2 1.5 Streptococcussanguis - antibiotic-susceptible clinical isolate 0.50 1.8 2.2 1.5Enterobacter sp - multi-drug resistant clinical isolate 0.06 0.2 0.1 0.2Proteus mirabilis - antibiotic-susceptible clinical isolate 0.06 0.2 0.30.4 Salmonella sp - multi-drug resistant clinical isolate 0.06 0.2 0.30.4 Klebsiella aerogenes NCTC11228 - antibiotic-susceptible type strain0.03 0.1 0.1 0.1 Escherichia coli ATCC25922 - antibiotic-susceptibletype strain 0.02 0.1 0.1 0.1 Serratia marcescens - multi-drug resistantclinical isolate 8.00 14.2 17.4 24.2 Enterococcus gallinarumvancomycin-resistant (VanC) clinical isolate 2.00 3.6 4.3 3.0 Proteusmirabilis - multi-drug resistant clinical isolate 2.00 3.6 4.3 6.1Klebsiella aerogenes - multi-drug resistant clinical isolate 1.00 1.82.2 6.3 Streptococcus oralis - antibiotic-susceptible clinical isolate1.00 1.8 2.2 1.5 Streptococcus oralis - macrolide-resistant clinicalisolate 1.00 1.8 2.2 1.5 Enterobacter sp - antibiotic-susceptibleclinical isolate 0.12 0.2 0.3 0.2 Serratia marcescens -antibiotic-susceptible clinical isolate 0.12 0.2 0.5 0.4

Specifically, Table 22a reports results in terms of dilution amounts toachieve an MID/MIC 50. Accordingly, for example, the number “ 1/64”under GR-05 for GP01 means that the original GR-05 solution was dilutedto 1/64^(th) its potency to achieve and MID/MIC50 for staphylococcusaureus ATCC-29213. The numbers under the columns “Levofloxacin”correspond to the amount of antibiotic in μg/ml required to achieve asimilar MID/MIC 50.

In contrast, the numbers reported in Table 22b are all reported inμg/ml. Additionally, the relative efficacy levels for three of the testsolutions relative to Levofloxacin are also reported. Wherever thereported number is 1.0 or greater, it means that the test solution wasas good as, or better, than the known antibiotic. Accordingly, a numberof “1.5” means that when the ppm of the solution is converted to “μg/ml”and the number of μg/ml (i.e., from the converted ppm) is divided intothe required μg/ml of the antibiotic needed to achieve an MIC/MID 50,1.5 times as much antibiotic is needed to achieve the same effect. Thus,many of the test solutions significantly outperformed this antibiotic.

Table 22c uses a format similar to that used for Table 22a, however, thetest solutions were tested against a variety of fungi. Again, the testsolutions were significantly diluted to achieve MID/MIC 50 values (e.g.,dilutions between ⅛^(th) and 1/128^(th)), showing that the testsolutions also have significant efficacy against fungi.

TABLE 22c MID/MIC mg/L GR- GR- GR- GR- GR- GR- GR- GR- GR- GR- GR- GR-Isolate Organism 05 05 08 08 21 21 01 01 24 24 25 25 NCPF 7147 Altemariaalternata-48 hrs 1/16 1/16 1/16 1/16 1/16 1/32 1/32 1/32 1/32 1/64 1/641/64 NCPF 2175 Aspergillus flavus-48 hrs 1/16 1/16 1/16 1/16 1/16 1/161/16 1/16 1/32 1/32 1/64 1/64 NCPF 2140 Aspergillus furnigatus-48 hrs1/16 1/16 1/16 1/16 1/16 1/16 1/32 1/32 1/32 1/32 1/64 1/64 NIH 2624Aspergillus terreus-48 hrs 1/32 1/32 1/32 1/32 1/32 1/32 1/64 1/64 1/641/64 1/128 1/128 NCPF 3309 Candida glabrata-48 hrs 1/16 1/16 1/16 1/161/16 1/16 1/16 1/16 1/32 1/32 1/32 1/32 NCPF 3516 Candida lusitaniae-48hrs 1/16 1/16 1/16 1/16 1/16 1/16 1/16 1/16 1/32 1/32 1/64 1/64 ATCC22019 Candida parapsilosis-48 hrs 1/32 1/32 1/32 1/32 1/32 1/32 1/161/16 1/64 1/64 1/64 1/64 NCPF 5011 Epidermophyton floccosum - 1/32 1/321/32 1/32 1/16 1/16 1/32 1/32 1/64 1/32 1/64 1/128 48 hrs NCPF 2722Fusarium oxysporum-48 hrs 1/16 1/16 1/8 1/8 1/8 1/8 1/16 1/16 1/16 1/161/32 1/32 NCPF 436 *Microsporum audounii-72 hrs 1/16 1/16 1/16 1/16 1/161/16 1/16 1/16 1/16 1/16 1/32 1/16 NCPF 177 *Microsporum canis-72 hrs1/32 1/32 1/16 1/16 1/16 1/16 1/16 1/16 1/32 1/32 1/64 1/32 NCPF 988*Microsporum ferrugineum- 1/8 1/8 1/8 1/8 1/8 1/8 1/8 1/8 1/8 1/8 1/161/16 72 hrs NCPF 2743 Mucor circinelloides-48 hrs 1/8 1/16 1/8 1/8 1/161/16 1/16 1/16 1/16 1/16 1/32 1/32 NCPF 2715 Penicillium chrysogenum-48hrs 1/16 1/16 1/16 1/16 1/16 1/16 1/32 1/32 1/32 1/32 1/64 1/64 NCPF7075 *Sprothrix schenkii-72 hrs 1/32 1/32 1/16 1/16 1/16 1/16 1/32 1/321/32 1/32 1/64 1/64 NCPF 175 Trychophyton interdigitale-72 hrs 1/8 1/81/8 1/8 1/8 1/8 1/8 1/8 1/16 1/16 1/32 1/32 NCPF 224 Trychophytonmentagrophytes- 1/16 1/16 1/16 1/16 1/16 1/16 1/16 1/16 1/16 1/16 1/321/32 48 hrs NCPF 118 Trychophyton rubrum-48 hrs 1/16 1/16 1/16 1/16 1/321/16 1/16 1/32 1/32 1/32 1/64 1/64 NCPF 3853 Trychophyton cutaneum-48hrs 1/32 1/32 1/16 1/16 1/32 1/32 1/32 1/32 1/32 1/64 1/64 1/64

MID/MIC mg/L GR- GR- Amphotericin Amphotericin Isolate Organism 26 26 BB NCPF 7147 Altemaria alternata-48 hrs 1/64 1/64 1 1 NCPF 2175Aspergillus flavus-48 hrs 1/32 1/32 4 4 NCPF 2140 Aspergillusfurnigatus-48 hrs 1/64 1/64 2 2 NIH 2624 Aspergillus terreus-48 hrs1/128 1/128 2 2 NCPF 3309 Candida glabrata-48 hrs 1/32 1/32 1 1 NCPF3516 Candida lusitaniae-48 hrs 1/32 1/32 1 1 ATCC 22019 Candidaparapsilosis-48 hrs 1/64 1/64 1 1 NCPF 5011 Epidermophyton floccosum-1/32 1/128 0.25 0.25 48 hrs NCPF 2722 Fusarium oxysporum-48 hrs 1/321/32 1 1 NCPF 436 *Microsporum audounii-72 hrs 1/32 1/32 0.5 0.5 NCPF177 *Microsporum canis-72 hrs 1/64 1/32 0.12 0.12 NCPF 988 *Microsporumferrugineum- 1/16 1/16 1 1 72 hrs NCPF 2743 Mucor circinelloides-48 hrs1/32 1/32 1 1 NCPF 2715 Penicillium chrysogenum-48 hrs 1/64 1/64 2 2NCPF 7075 *Sprothrix schenkii-72 hrs 1/64 1/64 1 1 NCPF 175 Trychophytoninterdigitale-72 hrs 1/16 1/16 2 2 NCPF 224 Trychophyton mentagrophytes-1/32 1/32 2 2 48 hrs NCPF 118 Trychophyton rubrum-48 hrs 1/64 1/64 0.5 1NCPF 3853 Trychophyton cutaneum-48 hrs 1/64 1/64 0.5 0.5

Example 19 Antiviral Efficacy of Solutions GR-05 and GR-08

The purpose of this Example was to evaluate the antiviral properties oftwo solutions, GR05 and GR-08 against duck Hepatitis B virus (i.e., as asurrogate virus for the human Hepatitis B virus) when exposed (insuspension) for the specified exposure period. The protocol utilized wasa modification of the Standard Test Method for Efficacy of VirucidalAgents Intended for Special Applications (ASTM E1052).

The LeGarth strain of duck Hepatitis B virus (DHBV) used for this studywas obtained commercially from Hepadnavirus Testing Inc., Palo Alto,Calif. and consisted of duck Hepatitis B virus serum obtained fromcongenitally infected ducklings. Virus aliquots were maintained at ≦−70°C. On the day of use, two aliquots were removed, thawed, combined andrefrigerated or stored on ice until used in the assay.

A suspension of primary duck hepatocytes was achieved following an insitu perfusion of the duck liver. The hepatocytes were seeded intosterile disposable tissue culture labware, maintained at 36-38° C. in ahumidified atmosphere of 5-7% CO₂ and used at the appropriate density.Only ducklings verified to be free of test virus were utilized in theassay.

The test medium used in this study was Leibovitz L-15 mediumsupplemented with 0.1% glucose, 10 μM dexamethasone, 10 μg/mL insulin,20 mM HEPES, 10 μg/mL gentamicin and 100 units/mL penicillin.

Table 23a lists the test and control groups, the dilutions assayed, andthe number of cultures used.

TABLE 23a Number of Dilutions and Cultures for Virucidal SuspensionStudy Cultures Dilutions Assayed per Total Test or Control Group (log₁₀)dilution Cultures Cell Control N/A 4 4/group Virus Control −2, −3, −4,−5, −6, −7 4 24 Sample lot #1 + virus −2, −3, −4, −5, −6, −7 4 24 Samplelot #2 + virus −2, −3, −4, −5, −6, −7 4 24 Cytotoxicity of lot #1 −2,−3, −4 2 6 Cytotoxicity of lot #2 −2, −3, −4 2 6 NeutralizationControl-lot #1 −2, −3, −4 2 6 Neutralization Control-lot #2 −2, −3, −4 26

A 4.5 mL aliquot of each of GR-05 and GR-08 was dispensed into separatesterile 15 mL conical tubes and mixed with a 0.5 mL aliquot of the stockvirus suspension. The mixtures were vortex mixed for a minimum of 10seconds and held for the remainder of the specified exposure times at37.0° C. The exposure times assayed was six hours. Immediately followingeach exposure time, a 0.5 mL aliquot was removed from each tube and themixtures were tittered by 10-fold serial dilutions (0.5 mL+4.5 mL testmedium) and assayed for the presence of virus.

A 0.5 mL aliquot of stock virus suspension was exposed to a 4.5 mLaliquot of test medium in lieu of test substance and treated aspreviously described. Immediately following each exposure time, a 0.5 mLaliquot was removed from the tube and the mixture was titered by 10-foldserial dilutions (0.5 mL+4.5 mL test medium) and assayed for thepresence of virus. All controls employed the FBS neutralizer asdescribed in the Treatment of Virus Suspension section. A virus controlwas performed for each exposure time. The virus control titer was usedas a baseline to compare the percent and log reductions of each testparameter following exposure to the test substances.

A 4.5 mL aliquot of each concentration of test substance was mixed with0.5 mL aliquot of test medium in lieu of virus and treated as previouslydescribed. The cytotoxicity of the cell cultures was scored at the sametime as virus-test substance and virus control cultures. Cytotoxicitywas graded on the basis of cell viability as determined microscopically.Cellular alterations due to toxicity were graded and reported toxic(“T”) if greater than or equal to 50% of the monolayer was affected.

Each cytotoxicity control mixture (above) was challenged with low titerstock virus to determine the dilution(s) of test substance at whichvirucidal activity, if any was retained. Dilutions that showed virucidalactivity were not considered in determining reduction of the virus bythe test substance.

As previously described, 0.1 mL of each test and control parameterfollowing the exposure period was added to fetal bovine serum (0.9 mL)followed immediately by 10-fold serial dilutions in test medium to stopthe action of the test substance. To determine if the neutralizer chosenfor the assay was effective in diminishing the virucidal activity of thetest substance, low titer stock virus was added to each dilution of thetest substance-neutralizer mixture. This mixture was assayed for thepresence of the virus (neutralization control above).

Primary duck hepatocytes were used as the indicator cell line in theinfectivity assays. Cells contained in cell culture labware wereinoculated in quadruplicate with 1.0 mL of the dilutions prepared fromthe input virus control, virus control and test substances. Thecytotoxicity and neutralization control dilutions were inoculated induplicate. Uninfected indicator cell cultures (negative cell controls)were inoculated with test medium alone. A 2.0 mL aliquot of test mediumwas added to each cell culture well. The inoculum was allowed to adsorbovernight at 36-38° C. in a humidified atmosphere of 5-7% CO₂. Followingthe adsorption period, a 3.0 mL aliquot of test medium was added to eachcell culture well. The cultures were incubated at 36-38° C. in ahumidified atmosphere of 5-7% CO₂ for ten days. The test medium wasaspirated from each test and control well and replaced with fresh mediumas needed throughout the incubation period. On the final day ofincubation, the cultures were scored microscopically for cytotoxicityand the cells were fixed with ethanol. An indirect immunofluorescenceassay was then performed using a monoclonal antibody specific for theenvelope protein of the DHBV.

Viral and cytotoxicity titers are expressed as −log₁₀ of the 50 percenttitration endpoint for infectivity (TCID₅₀) or cytotoxicity (TCD₅₀),respectively, as calculated by the method of Spearman Karber.

${{Log}\mspace{14mu} {of}\mspace{14mu} 1^{st}{dilution}\mspace{14mu} {inoculated}} - \left\lbrack {\left( {\left( \frac{{Sum}\mspace{14mu} {of}\mspace{14mu} \% \mspace{14mu} {mortality}\mspace{14mu} {at}\mspace{14mu} {each}\mspace{14mu} {dilution}}{100} \right) - 0.5} \right) \times \left( {{logarithm}\mspace{14mu} {of}\mspace{14mu} {dilultion}} \right)} \right\rbrack$  Percent  (%)  Reduction  Formula$\mspace{20mu} {{\% \mspace{14mu} {Reduction}}\mspace{14mu} = {{1 - {\left\lbrack \frac{{TCID}_{50}\mspace{14mu} {test}}{{TCID}_{50}\mspace{14mu} {virus}\mspace{14mu} {control}} \right\rbrack \times 100\mspace{20mu} {Log}\mspace{14mu} {Reduction}\mspace{14mu} {Formula}{Log}\mspace{14mu} {Reduction}}} = {{{TCID}_{50}\mspace{14mu} {of}\mspace{14mu} {the}\mspace{14mu} {virus}\mspace{14mu} {control}} - {{TCID}_{50}\mspace{14mu} {of}\mspace{14mu} {the}\mspace{14mu} {test}}}}}$

A valid test requires 1) that stock virus be recovered from the viruscontrol, 2) that the cell controls be negative for virus, and 3) thatnegative cultures are viable.

Test substance cytotoxicity was not observed at any dilution assayed(≦1.5 log₁₀). Under the conditions of this investigation, GR-05 andGR-08 demonstrated a ≧99.99% reduction in viral titer following a sixhour exposure time to duck Hepatitis B virus. The log reduction in viraltiter was ≧4.0 log₁₀. Specifically, Table 23b sets forth theexperimental results.

TABLE 23b Assay Results Effects of GR-05 and GR-08 Against DuckHepatitis B Virus as a Surrogate Virus for Human Hepatitis B Virus inSuspension Following a Six Hour Exposure Time Test: Duck Test: DuckHepatitis B Hepatitis B virus + virus + Virus Control NOG-5B-28TNOG-8B-27T Exposure Time Exposure Time Exposure Time Dilution 6 Hours 6Hours 6 Hours Cell Control 0 0 0 0 0 0 0 0 0 0 0 0 10⁻² + + + + 0 0 0 00 0 0 0 10⁻³ + + + + 0 0 0 0 0 0 0 0 10⁻⁴ + + + + 0 0 0 0 0 0 0 010⁻⁵ + + + + 0 0 0 0 0 0 0 0 10⁻⁶ 0 0 0 0 0 0 0 0 0 0 0 0 10⁻⁷ 0 0 0 0 00 0 0 0 0 0 0 TCID₅₀/0.1 mL 10^(5.5) ≦10^(1.5) ≦10^(1.5) Percent N/A≧99.99% ≧99.99% Reduction Log₁₀ N/A ≧4.0 log₁₀ ≧4.0 log₁₀ Reduction (+)= Positive for the presence of test virus (0) = No test virus recoveredand/or no cytotoxicity present (NT) = Not tested (N/A) = Not applicable

Table 23c sets forth the cytotoxicity and neutralization controlresults. As the date show, no cytotoxicity was measured for the GR-05and GR-08 solutions.

TABLE 23C Cytotoxicity and Neutralization Controls NeutralizationControl Duck Duck Cytotoxicity Control Hepatitis B Hepatitis B DilutionGR-05 GR-08 virus + GR-05 virus + GR-08 Cell Control 0 0 0 0 0 0 0 010⁻² 0 0 0 0 + + + + 10⁻³ 0 0 0 0 + + + + 10⁻⁴ 0 0 0 0 + + + + 10⁻⁵ NTNT NT NT 10⁻⁶ NT NT NT NT 10⁻⁷ NT NT NT NT TCID₅₀/0.1 mL ≦10^(1.5)≦10^(1.5) Neutralized Neutralized at ≦1.5 Log₁₀ at ≦1.5 Log₁₀ TCID₅₀/1.0mL TCID₅₀/1.0 mL (+) = Positive for the presence of test virus (0) = Notest virus recovered and/or no cytotoxicity present (NT) = Not tested

Example 20 Efficacy of GR-01, GR-05, GR-08 and GR-24 Against HumanAfrican Trypanosomiasis Parasites

Minimum Essential Medium (50 μl) supplemented according to Baltz et al.(1985) with 2-mercaptoethanol and 15% heat-inactivated horse serum wasadded to each well of a 96-well microtiter plate.

Serial drug dilutions were prepared covering a range from 90 to 0.123μg/ml.

Then 10⁴ bloodstream forms of Trypanosoma b. rhodesiense STIB 900 in 50μl were added to each well and the plate incubated at 37° C. under a 5%CO₂ atmosphere for 72 hours.

10 μl of Alamar Blue (12.5 mg resazurin dissolved in 100 mL distilledwater) were then added to each well and incubation continued for afurther 2-4 hours.

Then the plates were read with a Spectramax Gemini XS microplatefluorometer (Molecular Devices Cooperation, Sunnyvale, Calif., USA)using an excitation wave length of 536 nm and an emission wave length of588 nm.

Data were analysed using the software Softmax Pro (Molecular DevicesCooperation, Sunnyvale, Calif., USA). Decrease of fluorescence(=inhibition) was expressed as percentage of the fluorescence of controlcultures and plotted against the drug concentrations.

From the sigmoidal inhibition curves the IC50 values were calculated.

Cytotoxicity was assessed using the same assay and rat skeletalmyoblasts (L-6 cells). The medium used for the L-6 cells was RPMI 1640medium with 10% FBS and 2 mM L-glutamine.

TABLE 24a Total less Avg less 1 T.b. rhod. IC/50 most most Avg lessRelative Trial I II III IV V VI VII Total extreme extreme 1 ng/mlEfficacy Solution 0.99 0.071 0.059 0.134 0.325 0.146 0.008 1.733 0.7430.124 11 3× GR01 Solution 1.32 0.048 0.3 / / 0.055 / 1.723 0.403 0.13413 4× GR05 Solution 1.53 0.061 / / / 0.092 / 1.683 0.153 0.051 4 1× GR08Solution 0.344 0.054 0.06 / 0.41 0.083 / 0.951 0.541 0.135 17 5× GR24Melarsoprol 3 ng/ml / 2 ng/ml / 5 ng/ml / / 10 mg/ml 3.33 Mel. = controlIC50 expressed as % of the original solution received. / = no result

Example 21 Anti-Parasitic Efficacy of Solutions GR-01-GR-08

Efficacy testing of 10 solutions against the Plasmodium falciparum (3D7and Dd2 laboratory strains) occurred. The Anti-malarial activities ofthe ten solutions disclosed in Examples 1-5 (i.e., GR-01-GR-10) wereinvestigated with the primary aim of identifying the most promisingsolution through in vitro efficacy testing. A second objective was todetermine the anti-malarial activities of the same 10 solutions againsttwo different strains of Plasmodium falciparum (3D7 and Dd2 laboratorystrains) and to document any observable effect on the human erythrocytesused in the cultivation of the parasites.

The results show that all 10 solutions tested (i.e., GR-01-GR-10) hadanti-malarial activity with the effects being dose dependent. GR 08 hadthe best anti-malarial activity as it had the lowest IC₅₀ concentratingagainst both strains of parasites (i.e., 3.1 against 3D7; and 3.4against Dd2) used in this study in comparison with the other solutions.

Material and Methods In Vitro Cultivation of Malaria Parasite

Two laboratory strains of malaria parasites, chloroquine sensitive (3D7)and chloroquine resistant (Dd2) were used for these in vitro studies.Parasites were cultivated using methods by Trager and Jensen (1976) withslight modifications. In brief, parasites were removed from liquidnitrogen and thawed in a water bath set at 37° C. and immediatelycentrifuged at 2000 rpm for 7 minutes and the supernatants werediscarded. Equal volumes of thawing mix (3.5% NaCl in distilled water)were added and centrifuged as above and the supernatant discarded. Thecells were then washed two times in parasite culture medium and thecells added to a culture flask containing 5 ml parasite culture medium(RPMI 1640, L-glutamine, Gentamycin and Albumax) and 200 μl of freshlywashed human O+ red blood cells. The culture was then gassed for 30seconds using a gas mixture containing Oxygen 2.0% Carbon dioxide 5.5%and the remainder Nitrogen. Cultures were maintained for at least twoweeks continuously until a stable parasitaemia was obtained before beingused for the efficacy assay.

Preparation of the 10 Solutions for the Inhibition Assay

Serial dilutions (2 fold) of each solution were prepared starting from 2times dilution to 128 times dilution in parasite culture medium (RPMI1640, L-glutamine, Gentamycin and Albumax). In other words, 100 μl oftest solution was used per milliliter of culture mixture giving a startconcentration of 100 μl test solution/ml of culture medium (100 μl/ml).They were prepared prior to the start of the assays and keptrefrigerated until they were ready to be used.

Plasmodium falciparum Inhibition Assays

The ten different solutions were investigated for their anti-malarialactivities against two Plasmodium falciparum parasite strains (3D7 andDd2). Briefly, parasites were prepared from in vitro cultivation asdescribed above. Into each well of a 24-well culture plates was added 40μl of O+ freshly washed RBC at 1.0% parasitaemia in 900 μl of completeparasite medium. Into each of the wells, 100 μl of the diluted testsolutions (corresponding to 0.78 μl, 1.56 μl, 3.125 μl, 6.25 μl, 12.5μl, 25 μl, 50 μl, and 100 μl of the undiluted solution), were added perml of culture medium. Also included in each 24-well plate were wellscontaining 40 μl of uninfected RBC plus 100 μl of undiluted solution ofeach formulation and 40 μl of infected RBC (1.0%) without any of the tentest solutions. Assays were performed in triplicates. The plates werethen placed in a modular incubator chamber (California, USA) and gassedfor 10 minutes using a special gas mixture (Oxygen 2.0% Carbon dioxide5.5% and Nitrogen 92.5%). The chamber containing the plates wasincubated at 37° C. for 48 hours. At approximately 48 hours cultureswere removed and thin blood films prepared from each well on doublefrosted microscope slides. The slides were air-dried, fixed in methanoland stained with 10% giemsa in phosphate buffer.

Results and Discussion

The anti-malarial activities of all 10 solutions evaluated are shown inFIGS. 90A-90C, 91A-91C. All 10 solutions had anti-malarial activitiesthat were dose dependent. The percentage inhibition of the formulationsagainst chloroquine resistant P. falciparum strain (Dd2) at the highestconcentration (100 μl/ml) ranged between 62% and 82% (FIG. 90A). Forsolutions GR-05 and GR-08 the highest concentrations recorded 76% and83% inhibition, respectively. The lowest concentrations (0.78 μl testsolution/ml of culture mixture) were able to inhibit the P. falciparumgrowth by 16% and 34% for solutions GR-05 and GR-08, respectively (FIGS.90B and 90C).

Each of the 10 solutions also inhibited the growth of chloroquinesensitive strain of P. falciparum (3D7) parasites. The highestconcentration (100 μl test solution/ml) of the test solutions recorded amaximum inhibition ranging between 71% and 85% (FIG. 91B). SolutionsGR-05 and GR-08 recorded a maximum inhibition of 85% and 83%,respectively, while the lowest dilution used recorded 25% and 34%inhibition respectively (FIGS. 91B and 91C).

The growth inhibition characteristics of the ten solutions were similarto that observed for chloroquine (FIG. 92).

The concentration that inhibited the growth of each strain of P.falciparum (3D7 and Dd2) by 50% (IC₅₀) are presented in Table 25a. TheIC₅₀ values for the test solutions against chloroquine sensitive P.falciparum (3D7) parasites ranged from 3.1 μl/ml-6.2 μl/ml. Forchloroquine sensitive P. falciparum (Dd2) parasites the IC₅₀ ranged from3.4 μl/ml-7.9 μl/ml. GR-08 recorded the lowest IC₅₀ against bothchloroquine sensitive and chloroquine resistant strains of thePlasmodium parasites.

TABLE 25a IC 50 of all 10 test solutions against the 2 strains ofPlasmodium falciparum (3D7- chloroquine-sensitive strain and Dd2 -chloroquine-resistant strain) parasites Inhibition Concentration (IC50μ/ml) Solutions 3D7 Dd2 GR-01 GR 01 4.5 6.1 GR-02 GR 02 5.2 5.0 GR-03 GR03 4.9 5.9 GR-04 GR 04 4.6 7.9 GR-05 GR 05 4.1 4.9 GR-06 GR 06 6.2 5.9GR-07 GR 07 5.7 5.6 GR-08 GR 08 3.1 3.4 GR-09 GR 09 4.3 5.7 GR-10 GR 105.0 6.0

There were anti-malarial activities for all 10 test solutions. Theanti-malarial effects were dose dependent. The 10 test solutions did notshow observable adverse effects on infected and uninfected RBCs. GR-08had the lowest IC₅₀ against both chloroquine-resistant and chloroquinesensitive strains of Plasmodium parasites.

Example 22 Binding of Silver-Based Constituents in GR-05 to aPhospholipid Bilayer

This Example 22 demonstrates how the silver-based constituents in GR-05bind to a lipid bilayer membrane. Briefly, large unilamellar vesicleswere used as a membrane mimetic. Different amounts of vesicle solutionwere added to the GR-05 solution. After incubation of the mixture forabout one hour, the vesicles were centrifugally spun down to a pellet,leaving unbound silver constituents in the supernatant. Next, the silverconcentration (i.e., Ag ppm) in the supernatant was measured by theatomic absorbance spectrometer techniques discussed above herein. Themeasured concentration in the supernatant was compared to the silverconcentration in the control solution, where no vesicles were added, todetermine the amount of silver constituents from GR-05 that bound to thevesicles. Finally, the bound fraction of silver constituents was plottedagainst lipid concentration to determine the binding (equilibrium)constant.

Large unilamellar vesicles were prepared in the following manor: 50 mol% BrPC, 40 mol % POPC, 10 mol % POPG lipids, in original stock solutionin chloroform, were mixed together and were dried under a flowingnitrogen stream. Lipids were purchased from Avanti Polar Lipids, Inc.(Alabaster, Ala.) and were used without further purification. POPClipids (1-Palmitoyl-2-Oleoyl-sn-Glycero-3-Phosphocholine) are the mostcommonly used lipids for vesicle preparation. BrPC lipids(1,2-Dibromostearoyl-sn-Glycero-3-Phosphocholine) were used to make thevesicle bilayers more dense for easy centrifugal separation (i.e.,spinning down). Negatively charged POPG lipids(1-Palmitoyl-2-Oleoyl-sn-Glycero-3-[Phospho-rac-(1-glycerol)] (SodiumSalt)) were used to mimic the negative charged bilayer membranes ofbacteria. After the lipids were mixed together, they were rehydrated indeionized water to achieve a 5 mM total lipid concentration; and wereextruded multiple times through a 0.1 μm pore membrane (extruder andmembranes were purchased from Avanti Polar Lipids, Inc., Alabaster,Ala.) thus forming large unilamellar vesicles.

The binding of lipids to silver constituents in GR-05 can be describedin a first approximation with the following relationship:

$\begin{matrix}{{\alpha \; L} + {{{Ag}\overset{K}{}L_{\alpha}}{Ag}}} & (1)\end{matrix}$

where “α” is the number of lipids “L” that bind to a silver constituentin GR-05, thus forming a lipid-silver complex “L_(α)Ag”.

The binding constant, or equilibrium constant, K is given as:

$\begin{matrix}{K = \frac{\left\lbrack {L_{\alpha}{Ag}} \right\rbrack}{\lbrack L\rbrack^{\alpha}\lbrack{Ag}\rbrack}} & (2)\end{matrix}$

where [L_(α)Ag] is a concentration of bound silver constant, [L] is theconcentration of lipids, and [Ag] is the concentration of unbound silverconstituent. Total silver concentration [T_(Ag)] equals [L_(α)Ag] plus[Ag] and fraction of bound silver constituent ƒ_(B) is given as:

$\begin{matrix}\begin{matrix}{f_{B} = \frac{\left\lbrack {L_{\alpha}{Ag}} \right\rbrack}{\left\lbrack T_{Ag} \right\rbrack}} \\{= \frac{\left\lbrack {L_{\alpha}{Ag}} \right\rbrack}{\lbrack{Ag}\rbrack + \left\lbrack {L_{\alpha}{Ag}} \right\rbrack}} \\{= \frac{{K\lbrack L\rbrack}^{\alpha}\lbrack{Ag}\rbrack}{\lbrack{Ag}\rbrack + {{K\lbrack L\rbrack}^{\alpha}\lbrack{Ag}\rbrack}}} \\{= \frac{{K\lbrack L\rbrack}^{\alpha}}{1 + {K\lbrack L\rbrack}^{\alpha}}}\end{matrix} & (3)\end{matrix}$

While GR-05 also contains Zn-based constituents, as a firstapproximation, these were ignored for the purposes of this Example.

FIG. 93 shows that the binding of silver constituents from GR-05 followsan equilibrium curve described by a single equilibrium constant. Thisequilibrium constant suggest that two lipid molecules bind to a singlesilver constant, however, as noted above, zinc constituents from GR-05were not considered in this Example. However, this Example shows thatthe silver-based constituents from GR-05 clearly have a tendency tocomplex with the negatively based surfaces of the lipids provided.

1. A process for creating silver and zinc constituents in watercomprising: flowing chilled water through at least one first troughmember, said chilled water having an upper surface and a flow direction;providing at least one plasma-forming electrode comprising metallicsilver; creating at least one plasma between said at least oneplasma-forming electrode and at least a portion of said upper surface ofsaid chilled water; providing at least one set of electrodes comprisingsilver in contact with said chilled water and located downstream in saidflow direction from said at least one plasma-forming electrode;conducting at least one electrochemical reaction at said at least oneset of electrodes comprising silver to produce at least some silverconstituents within said chilled water; flowing a second water throughat least one second trough member, said second water having an uppersurface and a flow direction; providing at least one zinc electrode setcomprising a plasma-forming electrode comprising zinc and aliquid-contacting electrode comprising zinc; creating at least oneplasma between said at least one plasma-forming electrode comprisingzinc and at least a portion of said upper surface of said second waterto produce at least some zinc constituents in said second water fromsaid at least one zinc electrode set; mixing together said at least somesilver constituents within said chilled water and said at least somezinc constituents within said second water.
 2. The process of claim 1,wherein said chilled water has a temperature of about 2° C.
 3. Theprocess of claim 1, wherein said second water is heated and said heatedwater has a temperature of about 66° C.
 4. The process of claim 1,wherein said at least one first trough member comprises a conduit withat least one inlet and at least one outlet which permits said water toflow therein and said at least one second trough member comprises aconduit with at least one inlet and at least one outlet which permitssaid second water to flow therein.
 5. The process of claim 1, whereineach said at least one plasma comprises an adjustable plasma.
 6. Theprocess of claim 1, wherein each said at least one plasma-formingelectrode provides at least one species therefrom that is present insaid at least one plasma.
 7. The process of claim 1, wherein said atleast some silver constituents comprise metallic nanoparticles.
 8. Theprocess of claim 1, wherein said at least some silver constituentscomprise metallic ions.
 9. The process of claim 1, wherein said at leastsome zinc constituents comprise metallic ions.
 10. The process of claim1, wherein at least one first power source is connected electricallybetween said at least one set of electrodes comprising silver to causesaid at least one electrochemical reaction to occur within said water.11. The process of claim 1, wherein at least one first power source isprovided between said plasma-forming electrode comprising zinc, and saidliquid-contacting electrode comprising zinc to cause said at least oneelectrochemical reaction to occur.
 12. The process of claim 1, furthercomprising at least one control device for adjusting the location ofsaid at least one set of electrodes comprising silver relative to thesurface of the water.
 13. The process of claim 1, further comprising atleast one control device for adjusting the location of said at least onemetallic electrode set relative to the surface of the water.
 14. Theprocess of claim 12, wherein said at least one control device maintainsa substantially constant voltage across said at least one set ofelectrodes comprising silver by adjusting the amount of contact of saidelectrodes comprising silver with said flowing water.
 15. The process ofclaim 12, wherein said at least one control device maintains asubstantially constant voltage across said at least one zinc electrodeset by adjusting the location of said plasma-forming electrodecomprising zinc relative to the upper surface of said second water. 16.The process of claim 14, wherein said substantially constant voltage ismaintained within a range of 630-1550 Volts.
 17. The process of claim15, wherein said substantially constant voltage is maintained within arange of 600-1880 Volts.
 18. The process of claim 1, wherein said atleast one set of electrodes comprising silver comprises at least foursets of electrodes comprising silver.
 19. The process of claim 1,wherein said at least one zinc electrode set comprises at least foursets of electrodes comprising metallic zinc.
 20. The process of claim 1,wherein said at least one first trough member with said at least onesecond trough member together comprise a top portion of a “Y”-shape, andsaid at least some silver constituents and said at least some zincconstituents mix together at the bottom portion of the “Y”-shapedtrough.
 21. The process of claim 20, wherein another at least oneelectrode set comprising a plasma-forming electrode and aliquid-contacting electrode create at least one plasma in said baseportion of the “Y”-shaped trough.
 22. The process of claim 1, whereinsaid mixing together occurs by separately collecting outputs from eachof said first and second trough members and mixing together suchcollected outputs in another vessel.
 23. A process for creating silverconstituents in water and zinc constituents in water comprising: flowingwater through a first upper portion of a “Y”-shaped trough member, saidwater having an upper surface and a flow direction; providing at leastone plasma-forming electrode comprising metallic silver; creating atleast one plasma between said at least one plasma-forming electrode andat least a portion of said upper surface of said water; providing atleast one set of electrodes comprising silver in contact with said waterand located downstream in said flow direction from said at least oneplasma-forming electrode; conducting at least one electrochemicalreaction at said at least one set of electrodes comprising silver toproduce at least some silver constituents within said water; flowing asecond water through a second upper portion of a “Y”-shaped troughmember, said at least one second water having an upper surface and aflow direction; providing at least one zinc electrode set comprising aplasma-forming electrode comprising zinc and another electrodecomprising zinc in electrical connection with said plasma-formingelectrode through said second water; creating at least one plasmabetween each of said at least one plasma-forming electrode and at leasta portion of said upper surface of said second water to produce at leastsome zinc constituents from said at least one zinc electrode set in saidsecond water; mixing together at a base portion of said “Y”-shapedtrough member, said at least some silver constituents within said waterand said at least some zinc constituents within said second water. 24.The process of claim 23, wherein said mixing together of said water andsaid second water at said base portion of said “Y”-shaped trough membercreates a mixed water having an upper surface; and providing at leastone plasma-forming electrode in said base portion of said “Y”-shapedtrough member; and creating at least one plasma between said at leastone plasma-forming electrode and at least a portion of said uppersurface of said mixed water.
 25. A process for creating silver and zincconstituents in water comprising: flowing water through at least onefirst trough member, said water having an upper surface and a flowdirection; providing at least one plasma-forming electrode comprisingmetallic silver; creating at least one plasma between said at least oneplasma-forming electrode and at least a portion of said upper surface ofsaid water; providing at least one set of electrodes comprising silverin contact with said water and located downstream in said flow directionfrom said at least one plasma-forming electrode; conducting at least oneelectrochemical reaction at said at least one set of electrodescomprising silver to produce at least some silver constituents withinsaid water; flowing a second chilled water through at least one secondtrough member, said second chilled water having an upper surface and aflow direction; providing at least one zinc electrode set comprising aplasma-forming electrode comprising zinc and a liquid-contactingelectrode comprising zinc; creating at least one plasma between said atleast one plasma-forming electrode comprising zinc and at least aportion of said upper surface of said second chilled water to produce atleast some zinc constituents in said second chilled water from said atleast one zinc electrode set; mixing together said at least some silverconstituents within said water and said at least some zinc constituentswithin said second chilled water.
 26. The process of claim 25, whereinsaid at least some silver constituents comprise metallic nanoparticles.27. The process of claim 25, wherein said at least some silverconstituents comprise metallic ions.
 28. The process of claim 25,wherein said at least some zinc constituents comprise metallic ions. 29.The process of claim 25, further comprising at least one control devicefor adjusting the location of said at least one set of electrodescomprising silver relative to the surface of the water.
 30. The processof claim 29, wherein said at least one control device maintains asubstantially constant voltage across said at least one set ofelectrodes comprising silver by adjusting the amount of contact of saidelectrodes comprising silver with said flowing water.
 31. The process ofclaim 29, wherein said at least one control device maintains asubstantially constant voltage across said at least one zinc electrodeset by adjusting the location of said plasma-forming electrodecomprising zinc relative to the upper surface of said second water. 32.A process for creating silver and zinc constituents in water comprising:flowing water through at least one first trough member, said waterhaving an upper surface and a flow direction; providing at least oneplasma-forming electrode comprising metallic silver; creating at leastone plasma between said at least one plasma-forming electrode and atleast a portion of said upper surface of said water; providing at leastone set of electrodes comprising silver in contact with said water andlocated downstream in said flow direction from said at least oneplasma-forming electrode; conducting at least one electrochemicalreaction at said at least one set of electrodes comprising silver toproduce at least some silver constituents within said water; flowing asecond heated water through at least one second trough member, saidsecond heated water having an upper surface and a flow direction;providing at least one zinc electrode set comprising a plasma-formingelectrode comprising zinc and a liquid-contacting electrode comprisingzinc; creating at least one plasma between said at least oneplasma-forming electrode comprising zinc and at least a portion of saidupper surface of said second heated water to produce at least some zincconstituents in said second heated water from said at least one zincelectrode set; mixing together said at least some silver constituentswithin said water and said at least some zinc constituents within saidsecond heated water.
 33. A process for creating silver and zincconstituents in water comprising: flowing heated water through at leastone first trough member, said heated water having an upper surface and aflow direction; providing at least one plasma-forming electrodecomprising metallic silver; creating at least one plasma between said atleast one plasma-forming electrode and at least a portion of said uppersurface of said heated water; providing at least one set of electrodescomprising silver in contact with said heated water and locateddownstream in said flow direction from said at least one plasma-formingelectrode; conducting at least one electrochemical reaction at said atleast one set of electrodes comprising silver to produce at least somesilver constituents within said heated water; flowing a second chilledwater through at least one second trough member, said second chilledwater having an upper surface and a flow direction; providing at leastone zinc electrode set comprising a plasma-forming electrode comprisingzinc and a liquid-contacting electrode comprising zinc; creating atleast one plasma between said at least one plasma-forming electrodecomprising zinc and at least a portion of said upper surface of saidsecond chilled water to produce at least some zinc constituents in saidsecond chilled water from said at least one zinc electrode set; mixingtogether said at least some silver constituents within said heated waterand said at least some zinc constituents within said second chilledwater.